WO2006123759A1 - Catalyseur pour la polymerisation d'olefine, procede de production d’une polyolefine, procede de production d’un copolymere de propylene, polypropylene, composition de polypropylene, et leur utilisation - Google Patents

Catalyseur pour la polymerisation d'olefine, procede de production d’une polyolefine, procede de production d’un copolymere de propylene, polypropylene, composition de polypropylene, et leur utilisation Download PDF

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Publication number
WO2006123759A1
WO2006123759A1 PCT/JP2006/309972 JP2006309972W WO2006123759A1 WO 2006123759 A1 WO2006123759 A1 WO 2006123759A1 JP 2006309972 W JP2006309972 W JP 2006309972W WO 2006123759 A1 WO2006123759 A1 WO 2006123759A1
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WIPO (PCT)
Prior art keywords
propylene
group
carbon atoms
zirconium dichloride
olefin
Prior art date
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PCT/JP2006/309972
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English (en)
Japanese (ja)
Inventor
Yasushi Tohi
Masahiko Okamoto
Ryoji Mori
Tatsuya Nakamura
Takashi Yukita
Takashi Nakagawa
Miyuki Konno
Yuichi Yamamura
Shigenobu Ikenaga
Mayumi Hiwara
Naritoshi Hirota
Hiromasa Marubayashi
Kouji Nagahashi
Shiro Otsuzuki
Tomohiro Yamaguchi
Masashi Higuchi
Yasuo Ichiki
Original Assignee
Mitsui Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to CN2006800170896A priority Critical patent/CN101189269B/zh
Priority to KR1020117007628A priority patent/KR101187539B1/ko
Priority to EP06746639.1A priority patent/EP1900758B9/fr
Priority to KR1020117015073A priority patent/KR101169179B1/ko
Priority to KR1020107009102A priority patent/KR101064037B1/ko
Publication of WO2006123759A1 publication Critical patent/WO2006123759A1/fr
Priority to US11/984,440 priority patent/US9382356B2/en
Priority to US15/174,421 priority patent/US20160280819A1/en

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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C—CHEMISTRY; METALLURGY
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    • C08L23/10—Homopolymers or copolymers of propene
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    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08L2207/00—Properties characterising the ingredient of the composition
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    • C08L2207/12—Syndiotactic polypropylene
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/1397—Single layer [continuous layer]

Definitions

  • Catalyst for olefin polymerization method for producing olefin polymer, method for producing propylene copolymer, propylene polymer, propylene polymer composition and uses thereof
  • the present invention (1) relates to a catalyst for olefin polymerization comprising a bridged meta-octene compound having a specific structure, and a method for producing an olefin polymer using the catalyst for olefin polymerization.
  • the present invention (2) relates to a method for producing a propylene-based copolymer.
  • the present invention (3) relates to a propylene polymer and a molded product obtained from the polymer, and more particularly to a syndiotactic propylene polymer and a molded product obtained from the polymer.
  • the present invention (4) includes a propylene polymer composition, a molded article comprising the composition, a pellet comprising the propylene polymer composition, a modifier for a thermoplastic polymer comprising the pellet, thermoplasticity
  • the present invention relates to a method for producing a resin composition.
  • the present invention (5) relates to a propylene-based polymer composition and a molded article having the composition strength.
  • the present invention (6) relates to a propylene-based polymer composition and a molded body using the composition.
  • meta-mouth compound As a homogeneous catalyst for olefin polymerization, a so-called meta-mouth compound is well known.
  • isopropylidene (cyclopentagenyl) (9-fluorene) synthesized from a ligand obtained by crosslinking cyclopentagel and fluorenyl with isopropylidene is used as the ligand.
  • meta-acene compound that is a transition metal catalyst and aluminoxane power JA Ewen reported that propylene polymerization in the presence of a catalyst yielded a polypropylene with a high tacticity such that the syndiotactic pentad fraction exceeded 0.7 (non-patent Reference 2).
  • Patent Document 1 As an improvement of this meta-octene, an attempt has been made to improve stereoregularity by changing the fluorine to a 2,7-di-tert-butylfluoryl group (Patent Document 1).
  • Patent Document 2 attempts to improve stereoregularity by changing the fluorine to a 3,6-di-tert-butylfluoryl group (Patent Document 2), and combining cyclopentagel and fluorenyl.
  • Patent Documents 3 and 4 dimethylmethylene (3-tert-butylcyclopentagel) (fluorene) zirconium dichloride introduced with a methyl group at the 5-position of the cyclopentagel ring was also introduced. It is possible to obtain a higher molecular weight of isotactic polypropylene with (L-5-methylcyclopentagel) (fluorene) zirconium dichloride (Patent Document 5).
  • the propylene-based copolymer is a thermoplastic resin material! // is used as a modifier for thermoplastic resin in various applications.
  • a polymerization catalyst used when producing a propylene-based copolymer a titanium-based catalyst and a meta-octacene-based catalyst are known.
  • the meta-cene catalyst is excellent in copolymerization with ⁇ -olefin, and can be polymerized in a wide range of compositions.
  • the molecular weight does not increase when polymerized at high temperature, and the polymerization activity is low. There was a problem of power that could not be realized.
  • the present inventors as a result of intensive studies in view of such circumstances, the present inventors, as a result of using a specific transition metal catalyst, the obtained propylene copolymer has a high molecular weight and high-temperature polymerization. As a result of finding that it can be produced, the present invention (2) has been completed.
  • polypropylene includes, for example, isotactic polypropylene, syndiotactic polypropylene, etc.
  • isotactic polypropylene is inexpensive, rigid, Widely used in various applications because of its excellent heat resistance and surface gloss.
  • syndiotactic polypropylene is known to be obtained by low-temperature polymerization in the presence of a vanadium compound, an ether, and an organic aluminum catalyst.
  • the polymer obtained by this method is difficult to say, although it exhibits the syndiotactic nature of its low syndiotacticity.
  • JAEwen et al. Can obtain a polypropylene with the highest tacticity such that the syndiotactic pentad fraction exceeds 0.7 by using a transition metal catalyst having an asymmetric ligand and a catalyst having aluminoxane power. Since its first discovery (j.Am.Chem.Soc., 198 8,110,6255-6256 (Non-patent Document 2)), many achievements related to syndiotactic polypropylene have been published. For example, JP-A-8-67713 (Patent Document 8) discloses rac-2,2-dimethylpropylidene (1-7?
  • Syndiotactic polypropylene is much more transparent, has a higher surface gloss, and is more flexible than conventional isotactic polypropylene, so films, sheets, In addition to uses such as fibers, injection-molded products, and blow-molded products, new and powerful applications that could not be applied to isotactic polypropylene are expected.
  • the syndiotactic polypropylene obtained by the method described in the above publication has a problem that the crystallization speed is lower than that of the isotactic polypropylene and the molding processability is inferior because the crystallization temperature is low.
  • syndiotactic polypropylene is difficult to crystallize even during the pelletization stage during continuous operation and coupled with the low crystallization temperature, the time required to cool the injection molded product or extruded film or sheet is A much longer than isotactic polypropylene. This property controls the production speed of the compact. It was delayed, resulting in increased energy costs. In addition to the moldability, there was room for further improvement in terms of the balance of heat resistance, transparency, rigidity and strength as a molded body.
  • Patent Document 10 the peak intensity of a syndiotactic pentad bond in the spectrum of a methyl group measured by 13 C-NMR is proposed.
  • the composition had high syndiotacticity and was excellent in impact resistance and transparency.
  • JP-A-7-247387 Patent Document 11
  • 50 to 99 parts by weight of a syndiotactic polypropylene and 1 to 50 parts by weight of isotactic polypropylene 50 to 50 parts 99.9 parts by weight and a plasticizer 0.1 to 50 parts by weight A syndiotactic polypropylene resin composition is proposed.
  • the composition was able to obtain a molded article having excellent molding processability and transparency and flexibility, and had a high crystallization speed and excellent molding power.
  • syndiotactic polypropylene having a syndiotactic pentad fraction measured by 13 C-NMR of 0.7 or more is 97 to 99.99.
  • a syndiotactic polypropylene resin composition comprising 0.01% to 3% by weight of polyethylene and polyethylene is proposed. The composition was excellent in moldability and quick crystallization speed.
  • Patent Document 13 a syndiotactic polypropylene and a soft transparent syndiotactic polypropylene composition having an amorphous propylene ' ⁇ -olefin-based copolymer force are proposed. ing.
  • the composition was excellent in transparency, flexibility, scratch resistance, and heat resistance.
  • Patent Document 14 a soft and transparent syndiotactic composition containing syndiotactic polypropylene and a propylene / ethylene copolymer having a substantially syndiotactic structure.
  • a polypropylene composition is disclosed. It is described that the composition is excellent in transparency, flexibility, scratch resistance, and heat resistance.
  • any of the compositions described in any of the above-mentioned publications can be further improved in terms of a balance of formability, heat resistance, flexibility, scratch resistance, wear resistance, vibration damping, and the like. There was room for
  • Patent Document 1 Japanese Patent Laid-Open No. 46969394
  • Patent Document 2 Japanese Patent Laid-Open No. 2000-212194
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-189666
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-189667
  • Patent Document 5 Special Table 2001-526730
  • Patent Document 6 JP-A-2-274703
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-161957
  • Patent Document 8 JP-A-8-67713
  • Patent Document 9 Japanese Patent Laid-Open No. 4-802147
  • Patent Document 10 Japanese Patent Laid-Open No. 3-12439
  • Patent Document 11 Japanese Patent Laid-Open No. 7-247387
  • Patent Document 12 JP-A-8-59916
  • Patent Document 13 Japanese Patent Laid-Open No. 2000-191852
  • Patent Document 14 Japanese Unexamined Patent Publication No. 2000-191858
  • Non-Patent Document 2 Am. Chem. Soc., 1988, 110, 6255-6256
  • the problem to be solved by the present invention (1) is that a-olefin such as propylene is polymerized.
  • a high melting point and a sufficient molecular weight can be obtained not only at normal temperature but also at high temperature, and when a-olefin containing ethylene as a main component is polymerized at high temperature.
  • Another object of the present invention is to provide a catalyst for olefin polymerization which can obtain an ethylene polymer having good activity and a high molecular weight, that is, high performance for the production of a wide range of olefin polymers.
  • Another object of the present invention is to provide a method for producing an olefin polymer using such an olefin polymerization catalyst.
  • the problem to be solved by the present invention (2) relates to a method for producing a propylene copolymer, and a propylene copolymer having an excellent polymerization activity and a high molecular weight can be obtained and polymerization at a high temperature is possible. It is to provide a method for producing a propylene-based copolymer characterized by being
  • the problem to be solved by the present invention (3) is to provide a syndiotactic propylene copolymer improved in the above-mentioned problems and a molded product obtained therefrom. Specifically, it provides syndiotactic propylene polymers with excellent moldability by improving the crystallization speed and crystallization temperature, and has excellent heat resistance, transparency, rigidity, and tensile breaking strength. Another object is to provide a molded body.
  • the problem to be solved by the present invention (3) is to provide a propylene polymer composition excellent in moldability and heat resistance.
  • the problem to be solved by the present invention (5) is to solve the above-mentioned points, and is excellent in formability and heat resistance, and further in flexibility, transparency, and low-temperature impact resistance.
  • An object of the present invention is to provide an excellent composition and a molded article comprising the composition.
  • the problem to be solved by the present invention (6) is to solve the above-mentioned points, and To provide a propylene polymer composition excellent in formability and heat resistance, to provide a propylene polymer composition excellent in moldability, heat resistance, scratch resistance, wear resistance, and vibration damping properties. Furthermore, in addition to moldability, heat resistance, scratch resistance, wear resistance, and vibration damping properties, to provide a polypropylene polymer composition with excellent flexibility, and in addition to moldability and heat resistance, scratch resistance An object of the present invention is to provide a propylene-based polymer composition having excellent wear resistance, flexibility, and low temperature impact resistance.
  • (b-2) a compound that forms an ion pair by reacting with the above-mentioned bridged metaguchicene compound (a-1), and (b-3) an organoaluminum compound.
  • R 5 , R 8 , R 9 and R 12 are selected from hydrogen, hydrocarbon group, and silicon-containing forces, which may be the same or different.
  • R 6 , RR 1Q and R 11 are not hydrogen atoms but contain hydrocarbon groups or It is chosen from the basic group and can be the same or different
  • R 2 and R 3 may be bonded to each other to form a ring
  • the adjacent groups are mutually Join to form a ring.
  • R 13 and R 14 are atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group excluding a methyl group, and a silicon atom-containing group, and may be the same or different from each other.
  • the substituents may be bonded to each other to form a ring.
  • M is Ti, Zr or Hf
  • Y is carbon or silicon
  • Q is selected from a halogen, a hydrocarbon group, a lone ligand, and a neutral ligand capable of coordinating with a lone pair, which may be the same or different.
  • j is an integer of 1 to 4.
  • R 2 , R 3 and R 4 are preferably hydrogen! /.
  • the catalyst for olefin polymerization (1) of the present invention (1) preferably further comprises a carrier (c).
  • the method for producing an olefin polymer of the present invention (1) is a method of polymerizing one or more monomers having 2 or more carbon atoms (X-olefin monomer selected) in the presence of the olefin polymerization catalyst (1). is there.
  • the propylene copolymer (B1) is characterized in that propylene is polymerized in the presence of a powerful olefin polymerization catalyst (2) with at least one monomer selected from ⁇ -olefin and polyene force excluding propylene. It is a manufacturing method.
  • a powerful olefin polymerization catalyst (2) with at least one monomer selected from ⁇ -olefin and polyene force excluding propylene. It is a manufacturing method.
  • ⁇ -olefin propylene is not included in the ⁇ -olefin.
  • R 9 and R 12 are atoms or groups selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing basic force, and each may be the same or different.
  • R 6 and R 11 are the same atom or the same group selected as a hydrogen atom, a hydrocarbon group, and a silicon-containing basic force,
  • R 7 and R 1Q are the same atom or the same group selected as a hydrogen atom, a hydrocarbon group, and a silicon-containing basic force,
  • R 1q and R 11 are all hydrogen atoms at the same time
  • R 2 and R 3 may be bonded to each other to form a ring.
  • Adjacent groups among R 5 to R 12 may be bonded to each other to form a ring.
  • R 13 and R 14 are Ariru group having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon atoms, alkyl ⁇ aryl group having a carbon number of 6-4 0, Furuoroariru group having 6 to 20 carbon atoms, carbon atoms 7 to 40 fluoroalkylaryl group, 6 to 20 carbon chloroaryl group, 7 to 40 carbon chloro alkenoreanoleno group, 6 to 20 bromo aryleno group, 7 to 7 carbon atoms Selected from 40 bromoanolalkyl groups, 6 to 20 carbon aryl groups and 7 to 40 carbon alkyl groups, which may be the same or different.
  • At least one of R 13 and R 14 is an aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or a bromoaryl having 6 to 20 carbon atoms.
  • Group, bromoalkyl aryl group having 7 to 40 carbon atoms, odoaryl group having 6 to 20 carbon atoms A 7 to 40 carbon alkyloaryl group and a 7 to 40 fluoroalkylene group are selected,
  • M is Ti, Zr or Hf
  • Y is carbon or silicon
  • Q is the same or different combination of halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or nonconjugated gen, anion ligand, and neutral ligand capable of coordinating with a lone pair of electrons.
  • j is an integer of 1 to 4.
  • R 13 and R ′′ are each an aryl group having 11 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms.
  • R 6 and R 11 are the same group selected from a hydrocarbon group and a silicon-containing group
  • R 7 and R 1Q is the same group selected as a hydrocarbon group and a silicon-containing group
  • R 6 and R 7 may be bonded to each other to form a ring
  • R 1Q and R 11 are bonded to each other. You can form a ring.
  • R 2 , R 3 and R 4 are hydrogen.
  • the propylene-based copolymer produced (B1) includes the amount of a propylene component 95-51 mole 0/0, alpha - Orefin component ethylene, 1 At least one selected from butene, 4-methylpentene-1, 1-hexene, 1-octene, and 1-decene, which contains 5 to 49 mol% of the polyene component.
  • It is at least one selected from the group consisting of conjugated, non-conjugated gen and non-co-aggregated triene, and includes this in an amount of 0 to 20 mol% (provided that the a-olefin component and the polyene component total 5 to 49 mol 0) / 0 ).
  • the propylene-based copolymer produced (B1) includes the amount of a propylene component 95-51 mole 0/0, alpha - Orefin component ethylene, 1 Bute 1-Otaten, which is at least one selected from the group consisting of 5 to 49 mol%, and the polyene component having a norbornene skeleton and 4,8-dimethyl-1,4,8-decato Lien, 4 Echiriden-8-methyl-1,7-a Nonajen (EMND) forces at least one selected, which contains an amount of 0 to 20 mol 0/0 (where, alpha - Orefin component and Poryen component 5 to 49 mol 0/0 in total).
  • EMND Echiriden-8-methyl-1,7-a Nonajen
  • the molar fraction of the structural unit derived from ethylene is ⁇
  • the molar fraction of a-olefin having 4 or more carbon atoms is P.
  • the value of P / P is preferably 0 to 0.80.
  • the propylene-based copolymer (B1) is produced under conditions of a polymerization temperature of 40 ° C to 200 ° C and a polymerization pressure of 0.5 Mpa to 10 Mpa.
  • the amount of the structural unit from which propylene power is also derived exceeds 90 mol% (provided that the total amount of the structural units in the polymer (A) is 100 mol%).
  • the structural unit derived from propylene is more than 90 mol% to 100 mol% or less, and ethylene or 4 to 20 carbon atoms (X-olefin linker is selected.
  • the derived structural unit is Omol% or more.
  • syndiotactic propylene polymer satisfying the following requirements [1], [2-2], and [3], including an amount of less than 10 mol% (however, the total amount of structural units is 10 Omol%)
  • “propylene polymer” means propylene single weight. In some cases, it is used as a term encompassing not only the polymer but also the above-described copolymer with ⁇ -olefin. Also, the propylene polymer of the present invention is referred to as "syndiotactic propylene polymer ( ⁇ )". There is.)
  • the melting point (Tm) obtained from a differential scanning calorimeter (DSC) is 145 ° C or higher.
  • the melting point (Tm) obtained from a differential scanning calorimeter (hereinafter referred to as DSC) is 145 ° C or higher, and the heat of fusion ( ⁇ ) force is OmiZmg or higher.
  • syndiotactic propylene polymer (A) of the present invention has the following requirements:
  • the n-decane soluble part is less than 1% by weight (wt%).
  • syndiotactic propylene polymer (A) that satisfies the requirement [4] in addition to the requirements [1] to [3], particularly a syndiotactic propylene polymer ( ⁇ ') Sometimes called.
  • the syndiotactic propylene polymer ( ⁇ ) of the present invention has the above requirements [1] to [4].
  • the tensile elastic modulus is in the range of 500 to 2000 MPa.
  • the tensile strength at break is 20 MPa or more.
  • the needle penetration temperature is 145 ° C or higher.
  • a syndiotactic propylene polymer satisfying the requirements [a] to [ ⁇ ] in addition to the requirements [1] to [4], particularly a syndiotactic propylene polymer ( ⁇ ) sometimes called.
  • the present invention (3) also includes a molded product obtained from the above-mentioned syndiotactic propylene polymers ( ⁇ ), ( ⁇ ') and ( ⁇ ").
  • the propylene-based polymer composition of the present invention contains the syndiotactic propylene polymer ( ⁇ ).
  • the shaped product of the present invention (3) is obtained from the composition.
  • Propylene 'a -olefin copolymer (B2) 90-5 parts by weight (however, the sum of (AA) and (B2) is 100 parts by weight)
  • the polymer (AA) has the following requirement (a), and the copolymer (B2) has the following requirement (b).
  • Preferred embodiments of the propylene-based polymer composition (XI) according to the present invention (4) include: (ii) 50 to 95 parts by weight of syndiotactic propylene polymer; and (ii) propylene 'a -olefin.
  • a propylene-based polymer composition comprising 5 parts by weight or more and 50 parts by weight or less of a copolymer (herein, the total of (AA) and (B2) is 100 parts by weight)
  • composition (Xli) sometimes called "composition (Xli)"
  • (AA) Syndiotactic propylene polymer 10 parts by weight or more and less than 50 parts by weight;
  • B2 Propylene 'a -olefin copolymer more than 50 parts by weight and 90 parts by weight or less (where (AA) and ( B2) is 100 parts by weight)
  • composition (Xlii) t) (Hereinafter, this composition may be referred to as a composition (Xlii) t).
  • composition (XI), (Xli) or (Xlii) is (1) 110 ° C determined by a differential scanning calorimeter. It is preferable that the half crystallization time (t) in isothermal crystallization at 10 to be less than lOOOsec.
  • composition (XI), (Xli) or (Xlii) preferably has (2) a needle penetration temperature of 145 ° C or higher.
  • the propylene polymer composition (Xli) has (2) a needle penetration temperature of 145 ° C or higher, and (3) an Izod impact strength at 0 ° C of 50 jZm or higher, and (4) a tensile modulus of 100 MPa. It is particularly preferable that the internal haze value of a press sheet having a thickness of 1 mm is 50% or less.
  • the propylene polymer composition (Xlii) has (2) a needle penetration temperature of 145 ° C or higher, and (4) a tensile elastic modulus in the range of 1 MPa to 400 MPa, and (5) a thickness It is particularly preferable that the internal haze value of a 1 mm press sheet is 30% or less.
  • the syndiotactic propylene polymer (AA) is an extreme value measured in decalin at 135 ° C. It is preferable that the viscosity [r?] Is in the range of 0.1 to LOdLZg and the heat of fusion ( ⁇ H) determined by differential scanning calorimetry (DSC) is 40 mjZmg or more.
  • the propylene ' ⁇ -olefin polymer (B2) has a molecular weight distribution (MwZMn, Mn: number average molecular weight, Mw: weight average molecular weight) is preferably 3.5 or less.
  • the propylene-based polymer composition (Y) according to another embodiment of the present invention (4) is:
  • Needle penetration temperature is 145 ° C or higher
  • I tension elastic modulus is in the range of 100MPa to 2000MPa
  • the internal haze value of the lmm press sheet is 50% or less.
  • the propylene-based polymer composition according to still another aspect of the present invention (4) (Z) is 95.
  • Needle penetration temperature is 145 ° C or higher
  • the internal haze value of the lmm press sheet is 30% or less.
  • the molded article of the present invention (4) is obtained using the propylene polymer composition.
  • Propylene ⁇ ⁇ -olefin copolymer (B21) 99-35 parts by weight (however, the total of (AA1) and ( ⁇ 2 1) is 100 parts by weight)
  • the modifier for thermoplastic polymer of the present invention (4) comprises the pellets.
  • thermoplastic polymer composition of the present invention (4) is characterized in that the thermoplastic polymer modifier and a thermoplastic polymer are kneaded.
  • Syndiotactic propylene polymer ( ⁇ ) 100-25 parts by weight
  • Propylene ⁇ ⁇ -olefin copolymer ( ⁇ 2) 0-75 parts by weight (however, the sum of ( ⁇ ) and ( ⁇ 2) is 100 parts by weight)
  • the polymer (AA) satisfies the following requirement (a)
  • the copolymer (B2) satisfies the following requirement (b)
  • the copolymer (CO) satisfies the following requirement (c). Is characterized by:
  • Syndiotactic pentad fraction (rrrr fraction) force measured by 13 C-NMR is 3 ⁇ 45% or more and the melting point (Tm) determined by DSC is 145 ° C or more, and from propylene Containing the derived structural unit in an amount exceeding 90 mol% (provided that the total amount of the structural units in the polymer (AA) is 100 mol%);
  • That constituent units 10 to 45 mole 0/0 (provided that propylene mosquito ⁇ et guided constituent units and the number of 2-20 carbons is (X- Orefuin (except propylene) total 100 moles of the structural unit force is also directed in an amount of the 0/0), JIS K- compliant with 6721 by 230 ° C, measured boss was MFR of 0.5 at 2.16kg load 01: in the range of LOOgZlO min, and the following requirements ( satisfy one or more of b— 1) or (b 2);
  • Ethylene 'a-olefin copolymer (CO) for 100 parts by weight of total of (AA) and (B2)
  • composition (X2) (hereinafter, this composition may be referred to as “composition (X2i)”); (a): syndiotactic pentad component measured by 13 C-NMR The rate (rrrr fraction) power is 3 ⁇ 45% or more and the melting point (Tm) determined by DSC is 145 ° C or more, and 90 mol% of structural units derived from propylene (however, in the polymer (AA)) The total amount of the structural units of 100 mol%))
  • Propylene force is derived from at least one olefin that contains propylene power in an amount of 65-90 mol%, and also has 2-20 carbon atoms a-olefin (excluding propylene).
  • constituent units 10 to 35 mole 0/0 provided that propylene mosquito ⁇ excluding et guided constitutional units having a carbon number of 2-20 is the (X- Orefuin (except propylene) 100 molar sum of the forces directed a structural unit in an amount of 0/0 to), JIS K-compliant with the 6721 and 230 ° C, MFR is 0.
  • Syndiotactic pentad fraction (rrrr fraction) force measured by 13 C-NMR is 3 ⁇ 45% or more and the melting point (Tm) determined by DSC is 145 ° C or more, and from propylene Containing the derived structural unit in an amount exceeding 90 mol% (provided that the total amount of the structural units in the polymer (AA) is 100 mol%);
  • composition (X2), (X2i), or (X2ii) has, for example, (1) a half-crystallization time (t) in isothermal crystallization at 110 ° C determined by a differential scanning calorimeter is lOOOsec or less Is in the range
  • the composition (X2), (X2i) or (X2ii) preferably has, for example, (2) a needle penetration temperature of 145 ° C or higher.
  • the propylene 'a -olefin polymer (B2) has an intrinsic viscosity [7?] Measured in decalin of 135 ° C in the range of 0.1 to: LOdLZg, and has a molecular weight distribution determined by GPC ( MwZMn, Mn: Number average molecular weight, Mw: Weight average molecular weight) is preferably 3.5 or less.
  • the ethylene ' ⁇ -olefin copolymer (CO) has an MFR measured in a load of 2.16 kg at 190 ° C in accordance with JIS K-6721 of 0.01 to LOOgZlO. And the density is preferably from 0.910 to 0.850 (g / cm 3 ).
  • the molded product of the present invention (5) is characterized by using the propylene-based polymer composition (X2).
  • the propylene polymer composition (X3) of the present invention (6) is
  • the polymer ( ⁇ ) satisfies the following requirement (a), and the copolymer (B3) satisfies the following requirement (b):
  • Syndiotactic pentad fraction (rrrr fraction) force measured by 13 C-NMR is 3 ⁇ 45% or more and the melting point (Tm) determined by DSC is 145 ° C or more, and from propylene Containing the derived structural unit in an amount exceeding 90 mol% (provided that the total amount of the structural units in the polymer (AA) is 100 mol%);
  • composition ( ⁇ 3) As a preferred embodiment of the propylene polymer composition ( ⁇ 3) of the present invention (6) (hereinafter simply referred to as “composition ( ⁇ 3)”),
  • composition (X3i) From a total of 100 parts by weight of the syndiotactic propylene polymer ( ⁇ ) and the propylene ′ ⁇ -olefin copolymer ( ⁇ 3), (C1) from rosin-based resin, terpene-based resin and petroleum resin
  • a preferred embodiment of the propylene polymer composition (X3) of the present invention (6) is as follows:
  • Non-crosslinked or partially crosslinked olefin thermoplastic elastomer with respect to a total of 100 parts by weight of the syndiotactic propylene polymer (AA) and propylene'-olefin copolymer (B3).
  • the propylene polymer composition according to claim 1 comprising 0.1 to 500 parts by weight of one (C2) (hereinafter, this composition may be referred to as “composition (X3ii)”).
  • the syndiotactic propylene polymer (AA) has an intrinsic viscosity [7?] Measured in decalin at 35 ° C of 0.1 to: LOdLZg
  • the heat of fusion ( ⁇ ⁇ ) determined by differential scanning calorimetry (DSC) measurement should be 40mjZmg or more. preferable.
  • composition (X3)! / The molecular weight distribution determined by GPC of the propylene 'a -olefin polymer (B3) (MwZMn, Mn: number average molecular weight, Mw: weight average molecular weight) Is preferably 3.5 or less.
  • the shaped product of the present invention (6) is composed of the composition (X3).
  • the melting point is not only at room temperature but also at high temperature.
  • ⁇ -olefins having a high molecular weight and a sufficiently high molecular weight can be obtained with good activity, and ⁇ -olefins containing at least a part of ethylene were polymerized under the high temperature conditions using the same catalyst.
  • ethylene polymers with good activity and sufficiently high molecular weight can be obtained, that is, they exhibit high performance for the production of a wide range of olefin polymers.
  • an ⁇ -olefin polymer having a high melting point and a sufficiently high molecular weight can be obtained with good activity even under high temperature conditions. Even when ⁇ -year-old olefin containing at least a part of ethylene is polymerized under the high temperature conditions using the same catalyst, an ethylene-based polymer having a good activity and sufficiently high strength is obtained. be able to.
  • a propylene copolymer (B1) having excellent copolymerization performance and high molecular weight can be obtained by the method for producing the propylene copolymer (B1).
  • the propylene copolymer can be produced efficiently by allowing polymerization at a higher temperature than existing olefin polymerization catalysts. Can do.
  • a molded body can be provided.
  • the composition containing the syndiotactic propylene polymer ( ⁇ ) of the present invention (3) has moldability, Excellent heat resistance.
  • a molded product obtained from the composition containing the syndiotactic propylene polymer (A) of the present invention has excellent heat resistance.
  • the propylene polymer composition of the present invention (4) is excellent in moldability and heat resistance, and further has transparency.
  • the molded product of the present invention (4) is excellent in heat resistance, and is also excellent in transparency, flexibility and scratch resistance.
  • thermoplastic polymer composition excellent in moldability and heat resistance, and excellent in flexibility, transparency and scratch resistance can be obtained.
  • thermoplastic polymer modifier of the present invention (4) By using the thermoplastic polymer modifier of the present invention (4), a thermoplastic polymer composition having excellent moldability and heat resistance, and excellent flexibility, transparency and scratch resistance is obtained. be able to.
  • the production method of the thermoplastic resin composition of the present invention (4) is excellent in moldability and heat resistance, and is excellent in productivity with a thermoplastic polymer composition excellent in flexibility, transparency and scratch resistance. Can be manufactured.
  • the propylene-based polymer composition (X2) of the present invention (5) is excellent in moldability and heat resistance, and further excellent in transparency, flexibility and low-temperature impact resistance.
  • the molded product of the present invention (5) is excellent in heat resistance and further excellent in transparency, flexibility and low-temperature impact resistance.
  • the propylene polymer composition (X3) of the present invention (6) is excellent in moldability and heat resistance!
  • the propylene-based polymer composition of the present invention (6) (X3) is, P (mol 0/0) a proportion of the structural unit derived from ethylene, configuration from a one year old Refuin having 4 to 20 carbon atoms The unit percentage is P
  • the propylene polymer composition (X3) of the present invention (6) has at least one resin selected from the group consisting of rosin resin, terpene resin and petroleum resin added. When it is, it is excellent in formability, heat resistance, scratch resistance, wear resistance, vibration damping and flexibility.
  • the propylene-based polymer composition (X3) of the present invention (6) has moldability, heat resistance, scratch resistance, and wear resistance flexibility when a thermoplastic elastomer is added. Excellent in low temperature impact resistance.
  • FIG. 3 Relationship between MFR and [ ⁇ ] for the polymer corresponding to component (AA) or component (B2) used in the present invention (4) and (5) and the isotactic propylene polymer. This is a plot of. The part surrounded by the thick line indicates the region defined by requirement (b-2), which is one of the preferable properties of the component ( ⁇ 2) used in the present inventions (4) and (5). Indicates a preferred range of (b — 2).
  • FIG. 4 A plot of the relationship between MFR and [ ⁇ :] for a polymer corresponding to component (AA) or (B3) used in the present invention (6) and a isotactic propylene polymer. It is.
  • the part surrounded by the bold line indicates the area defined by requirement (b-2), which is one of the preferred properties of the component ( ⁇ 3) used in the present invention (6), and the broken line is ( b—Shows the preferred range of 2).
  • an olefin polymerization catalyst containing the crosslinked meta-orthocene compound (a-1) and the crosslinked meta-orthocene compound (a-1) used in the olefin polymerization catalyst (1) of the present invention (1) (1)
  • the best mode for carrying out the invention will be sequentially described with respect to a method for polymerizing olefin in the presence of the olefin polymerization catalyst (1).
  • the crosslinked meta-mouth compound (a-1) represented by the general formula [1-1] (hereinafter also referred to as “component (a-1)”) has a chemical structure. It has the following features [ml-1] to [ml-2].
  • transition metal (M) constituting the meta-mouth compound is titanium, zirconium or hafnium.
  • the cyclopentagel group may or may not be substituted.
  • Substituted ⁇ succinyl pentagel group means that the cyclopentagenyl group in the general formula [1-1] is R 2 , R 3 and R 4 are all cyclopentagel groups which are hydrogen atoms, and the substituted cyclopentagel group is Any one or more of R 2 , R 3, and R 4 may be a hydrocarbon group (f 1) or a cyclopentadienyl group substituted with a silicon-containing group (f 2). When two or more of R 3 and R 4 are groups other than hydrogen atoms, these groups may be the same or different from each other.
  • hydrocarbon group (fl) used for RR 4 the substituent group together with other substituent groups
  • a hydrocarbon group having a total carbon number of 20 to 20 hereinafter also referred to as “hydrocarbon group (f 1 ′)”.
  • R 2 and R 3 are hydrocarbon groups (f 1)
  • R 2 and R 3 are bonded to each other to form a ring (hereinafter also referred to as "ring (f"')"). May also be mentioned.
  • ring (f"') a ring
  • R 1 -R 4 only R 2 and R 3 form a ring.
  • the point power that can produce highly stereoregular, for example, syndiotactic poly-a-olefin is more preferable.
  • the preferable carbon number of each of R 2 and R 3 is 1 to 20 as described above.
  • the total number of carbon atoms of the two substituents forming the ring is preferably 2 to 40, more preferably 3 to 30, and further preferably 4 to 20.
  • the substituents R 2 and R 3 are bonded to each other to form a ring, some of the hydrogen atoms directly bonded to the carbon of the substituent are halogen atoms, oxygen-containing groups, nitrogen
  • the total number of carbon atoms of the two substituents forming the ring includes the oxygen-containing group, the nitrogen-containing group, and the silicon-containing group. Include the number of carbons in the group.
  • the hydrocarbon group having 1 to 20 carbon atoms (fl ') is an alkyl group, an alkenyl group, an alkynyl group or an aryl group composed only of carbon and hydrogen.
  • the hydrocarbon group having 1 to 20 carbon atoms in total includes these carbons in addition to an alkyl group, an alkyl group, an alkyl group, and an aryl group composed only of carbon and hydrogen. Also included are heteroatom-containing hydrocarbon groups in which some of the hydrogen atoms directly connected to are substituted with halogen atoms, oxygen-containing groups, nitrogen-containing groups, or silicon-containing groups.
  • Such hydrocarbon groups (fl ′) include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl.
  • Linear hydrocarbon groups such as n-octyl group, n-nor group, n-deoxy group;
  • Cyclic unsaturated hydrocarbon groups such as a phenol group, a naphthyl group, a biphenyl group, a phenanthryl group and an anthracyl group, and their nuclear alkyl substituents;
  • the key group-containing group (f 2) is a group having a key atom covalently bonded to the ring carbon of the cyclopentagel group, specifically an alkylsilyl group or a arylsilyl group.
  • a preferable group (f 2) when the substituent does not form a ring with other substituents, the group (f 2) having a total carbon number of 1 to 20 '), And examples thereof include a trimethylsilyl group and a triphenylsilyl group.
  • R 1 and R 4 are the same atom or the same group, and R 2 and R 3 are combined to form a ring or the same force. Atom or the same group is preferred R 1 and R 4 are more preferably hydrogen atoms It is particularly preferred that all of R 3 and are hydrogen atoms.
  • R in the general formula [1-1] The first important point in the fluorenyl group moiety in the chemical structural formula represented by the general formula [1-1] used in the polymerization method of the present invention (1) is that R in the general formula [1-1]
  • the four groups of 6 , R 7 , R 10 and R 11 are not hydrogen atoms.
  • R 6 , R U is selected from a hydrocarbon group and a silicon-containing group, and may be the hydrocarbon group (fl) or the silicon-containing group ( ⁇ ).
  • the second important point in the fluorenyl group portion is that R 6 and R 7 and R 1Q and R 11 do not bind to each other to form a ring.
  • the bridged metallocene compound (aI) used in the present invention (1) the four groups R 1Q and R 11 are not hydrogen atoms and R 7 and R 1Q and R 11 are not bonded to each other to form a ring, thereby achieving a strong polymerization activity that cannot be achieved with existing polymerizations. —It has become possible to produce polyolefin polymers such as propylene polymers.
  • R 5 , R 8 , R 9 and R 12 are each an atom or group selected from hydrogen, a hydrocarbon group (fl) and a silicon-containing group (12), which may be the same or different.
  • the adjacent groups are mutually Join to form a ring.
  • the substituent R 5 to R 12 hydrocarbon group used in (f 1), the substituents, if a group not forming a ring with another substituent, the total carbon number A hydrocarbon group (hydrocarbon group (f 1 ′)) of 1 to 20 can be preferably exemplified.
  • the substituents R 5 to R 12 are hydrocarbon groups (fl)
  • the substituent is the other adjacent substituents of the substituents R 5 to R 12 and the combination of the adjacent groups. In some cases, they may be bonded to each other within a range to form a ring. In this case, adjacent substituents among R 5 to R 12 are bonded to each other to form a ring (ring (f "')).
  • the substituents R 5 to R 12 are bonded to each other to form a ring within the range of the adjacent group combination, the substituents R 5 to R 12 It is preferable that two adjacent members are bonded to each other to form a ring.
  • each of R 5 to R 12 described above preferably has 1 to 20 carbon atoms.
  • the total number of carbon atoms of the two substituents formed is preferably 2 to 40, more preferably 3 to 30, and even more preferably 4 to 20.
  • R 6 and R 11 are the same atom or It is preferable that R 7 and R 1Q are the same atom or the same group.
  • Preferred groups as the hydrocarbon group (fl) are the above-described hydrocarbon groups having 1 to 20 carbon atoms (fl ′) and a ring structure ( ⁇ ′).
  • Preferred examples of the silicon-containing group (12) include The substituent is not shared with other substituents.
  • the C-containing group ( ⁇ ′) having 1 to 20 carbon atoms in total.
  • hydrocarbon group If it is a hydrocarbon group and does not form a ring with an adjacent group, it is independently a hydrocarbon group having 2 or more carbon atoms, more preferably 3 or more, and particularly preferably 4 or more.
  • Each is a group containing a cage.
  • a key-containing group having a total number of carbon atoms and key atoms of 3 or more, preferably 4 or more is preferable.
  • R 6 when R 6 is a hydrocarbon that does not form a ring with an adjacent group, and R 7 is a hydrocarbon group that does not form a ring with an adjacent group, , R 6 preferably has the same or more carbon number than R 7 .
  • R 6 is a key group and R 7 is a key group
  • the total number of key atoms and carbon atoms in R 6 is the total number of key atoms and carbon atoms in R 7
  • R 6 is a hydrocarbon group that does not form a ring with an adjacent group
  • R 7 is a key group
  • the number of carbon atoms in R 6 is the same as that of the carbon atom in R 7.
  • it is equal to or greater than the total number of atoms.
  • R 6 is a silicon-containing group and R 7 is a hydrocarbon group that does not form a ring
  • the total number of carbon atoms and carbon atoms in R 6 is equal to or equal to the number of carbon atoms in R 7. The above is preferable.
  • R 6 and R 11 are preferably an aryl group or a substituted aryl group, specifically, a phenol group, a 0-tolyl group, an m-tolyl group, a p-tolyl group, or a t-butylfuryl group.
  • R 6 and R 11 of the substituted fluorenyl group are either 1) or 2) above, carbon having a higher melting point and a molecular weight equal to or higher than that of the conventional polymer under the same polymerization conditions
  • An ⁇ -olefin polymer having a number of 3 or more can be obtained, or when compared with the same polymerization conditions not only under normal temperature polymerization conditions but also under high temperature polymerization conditions, the melting point is equal to or higher than the conventional one and the number of carbon atoms is high.
  • the above-described a-olefin polymer is also obtained, and an a-olefin polymer with particularly excellent performance balance can be produced.
  • the main chain part of the bond connecting the cyclopentagel group and the substituted fluorenyl group is a divalent covalent bond containing one carbon atom or one key atom.
  • cross-linking atom Y in the general formula [1-1] is R 13 , R 14 and these are hydrogen atoms
  • R 13 and R 14 are each preferably a hydrocarbon group other than a methyl group or a silicon-containing group.
  • R 13 and R 14 "Is preferably a hydrocarbon group other than a methyl group.
  • Y is carbon and R 13 and R 14 have a hydrocarbon group having 2 to 20 carbon atoms.
  • Examples of the hydrocarbon group other than methyl group used in R 13, and R 14, are bonded with R 13 and R 14 are mutually form a ring, Do, when the total carbon number Preferred examples include hydrocarbon groups of 2 to 20 (hereinafter also referred to as “hydrocarbon groups (fl”) ”). R 13 and R 14 are carbonized. Examples of the hydrogen group include a case where R 13 and R 14 are bonded to each other to form a ring (ring ( ⁇ ”)).
  • the hydrocarbon group having 2 to 20 carbon atoms (fl ) is obtained by removing a methyl group from a hydrocarbon group having 1 to 20 carbon atoms (fl ').
  • R 13 and R 14 are bonded to each other to form a ring, the above-mentioned R 13 and R "each have 2 to 20 carbon atoms, preferably in the range specification. Regardless, it is preferable that the total force of carbons of R 13 and R ′′ forming the ring structure is 40.
  • This ring structure is also one of the preferred embodiments like the hydrocarbon group.
  • a part of the hydrogen atoms directly bonded to the carbon of R 13 or R 14 is a halogen atom, an oxygen-containing group
  • the total number of carbon atoms of the plurality of substituents forming the ring may be the oxygen-containing group, the nitrogen-containing group, or the carbon-containing group. Include the number of carbons in the containing group.
  • the hydrocarbon group (fl ”) includes, for example, an alkyl group, a substituted alkyl group (including no- and rogen-substituted alkyl groups), a cycloalkyl group, and a substituted cycloalkyl group (including no- and rogen-substituted alkyl groups).
  • substituted aryl groups including halogen-substituted aryl groups and halogenated alkyl group-substituted aryl groups.
  • the substituent may be bonded to the aryl moiety or may be bonded to the alkyl moiety.
  • the key group-containing group (12) is a group having a key atom covalently bonded to the ring carbon of the cyclopentadenyl group, specifically an alkylsilyl group or a arylsilyl group.
  • the C 1 -C 20 -containing group ( ⁇ ′) includes a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group. Examples include groups.
  • Alkyl groups such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; , Aryl groups such as biphenyl group and naphthyl group; alkylaryl groups such as o-tolyl group, m-tolyl group and p-tolyl group;
  • Arylalkyl groups such as benzyl and pentene groups
  • the aryl group is preferably located at the meta position and the Z or para position.
  • an alkyl group, an arylalkyl group, a substituted arylalkyl group (including a halogenated alkylaryl group, a halogenated alkyl group-substituted arylalkyl group) and an alkylaryl group are more preferable.
  • an ⁇ -olefin polymer having a higher melting point and a higher molecular weight can be produced at a temperature equal to or higher than room temperature in consideration of the above characteristics.
  • crosslinked meta-mouth compound (a-1) used in the present invention (1) those in which R 13 and R 14 are the same are preferred because of their ease of production. used.
  • Q is halogen, a hydrocarbon group having 1 to 10 carbon atoms, neutral, conjugated or non-conjugated gen, er-on ligand, and isolated carbon number S 10 or less
  • the neutral ligands that can be coordinated by an electron pair are selected from the same or different combinations.
  • Specific examples of halogen include fluorine, chlorine, bromine and iodine.
  • hydrocarbon groups Methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropinole, 2,2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1-methylpropyl, 1 , 1, 2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1 -Cyclohexyl etc. are mentioned.
  • neutral, conjugated or non-conjugated genes having 10 or less carbon atoms include s-cis- or S-trans -'- 1,3-butadiene, S-cis- or S-trans- ? 7 4 - 1,4-diphenyl - 1,3-butadiene, s- cis - or s- trans - 4-3-methyl-1,3-Pentajen, s- cis - or S- trans -? 7 4 - 1,4-dibenzyl-1,3-butadiene, S-cis- or S-trans-7?
  • cation ligand examples include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.
  • j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.
  • Group 4 transition metal compound represented by the general formula [1-1] are shown below, but the scope of the present invention (1) is not particularly limited by this.
  • Dibenzylmethylene (cyclopentagel) (2,7-dimethyl-3,6-di tert-butylfluorenyl) zirconium dichloride [others include 1,3-diphenylisopropylidene (cyclopentadiene) ) (2,7-dimethyl-3,6-di tert-butylfluoryl) zirconium dichloride.
  • dibenzylmethylene (cyclopentagel (2,7-di (2,4,6-trimethylphenol) -3,6-ditert-butylfluoryl) zirconium dichloride
  • dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluoro) zirconium dichloride
  • dibenzylmethylene (cyclopentagel) (2,7-di (3 , 5-dimethylphenol) -3,6-di tert-butylfluoride) zirconium dichloride
  • dibenzylmethylene (cyclopentagenyl) (2,3,6,7-tetratert-butylfluorenyl) Zirconium dichloride
  • dibenzylmethylene (cyclopentagel) (2,7-di (4-methylphenol) -3,6-di tert-butylfluoryl) zirconium dichloride, dibenzyl
  • the (a-1) crosslinked meta-mouth compound can be produced by a known method, and the production method is not particularly limited.
  • a known production method for example, the production methods described in W02 001Z27124 and WO2004Z087775 by the applicant of the present invention can be mentioned.
  • meta-mouth compounds can be used alone or in combination of two or more.
  • the catalyst component is
  • (b) (b-1) an organoaluminum oxide compound, (b-2) a compound that forms an ion pair by reacting with the above-mentioned bridged metamouth compound (a-1), and (b- 3) At least one compound selected from organoaluminum compounds (also referred to herein as “component (b)”)
  • organoaluminum compound (b-1) also referred to as “component (b-1)” in the present specification
  • component (b-1) conventionally known aluminoxanes can be used as they are.
  • R is independently a hydrocarbon group having 1 to 10 carbon atoms, and ⁇ is an integer of 2 or more.
  • R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.
  • R is a methyl group.
  • n is 3 or more, preferably 10 or more.
  • a characteristic property in the high temperature solution polymerization of the present invention (1) is that a benzene-insoluble organoaluminum compound as exemplified in JP-A-2-78687 can also be applied. Further, it has an organoaluminum compound described in JP-A-2-167305, two or more types of alkyl groups described in JP-A-2-24701, JP-A-3-103407. Aluminoxane and the like can also be suitably used.
  • “Benzene-insoluble” organoaluminum compound means that A1 component dissolved in benzene at 60 ° C is usually 10% or less, preferably 5% or less, particularly preferably 2% in terms of A1 atom. The following refers to an organoaluminum compound that is insoluble or hardly soluble in benzene.
  • examples of the organoaluminum compound (b-1) include a modified methylaluminoxane represented by the following formula [4].
  • R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more.
  • This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum.
  • Such modified methylaluminoxane is Generally called MMAO!
  • MMA0 can be prepared by the methods listed in US4960878 and US5041584.
  • Tosoh Finechem Co., Ltd., etc. which are prepared using trimethylaluminum and triisobutylaluminum and R is an isopropyl group, are commercially produced under the names MMAO and TMAO.
  • Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, it is insoluble in benzene such as the compounds represented by the above formulas [2] and [3]. Or, unlike insoluble aluminoxane, it dissolves in aliphatic and alicyclic hydrocarbons.
  • organoaluminum compound (b-1) examples include an organoaluminum compound containing boron represented by the following general formula [5].
  • R d may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or a carbon atom.
  • ⁇ represents 10 hydrocarbon groups.
  • (b-2) Bridged metamouth compound (a-1) Compound that forms ion needles on the other hand Compound that reacts with bridged metamouth compound ( a -l) to form ion pairs (b-2)
  • the “ion compound (b-2)” or “component (b-2)” may be abbreviated as JP-A-1-501950 and JP-A-1-502036.
  • heteropoly compounds and isopoly compounds can also be mentioned.
  • the ionic compound (b-2) preferably employed is a compound represented by the following general formula [6].
  • R e + includes H +, a carbanium cation, an oxo-um cation, an ammonium cation, a phospho-mu cation, a cycloheptyl aryl cation, and a phlegm cation cation having a transition metal.
  • ⁇ Are organic groups, preferably aryl groups, which may be the same or different from each other.
  • carb cation examples include triphenyl carb cation, tris (methyl phen) carb cation, tris (dimethyl phen) carb cation and the like. Um cations and the like.
  • ammonium cation examples include trimethyl ammonium cation, triethyl ammonium cation, tri (n-propyl) ammonium cation, triisopropyl ammonium cation, tri (n-butyl) ammonium cation, and tri (n-butyl) ammonium cation.
  • Trialkylammonium cations such as isobutylammonium cation, ⁇ , ⁇ -dimethyl arium cation, ⁇ , ⁇ -jetyl arium cation, ⁇ , ⁇ - 2,4,6-pentamethylarium cation, etc.
  • dialkyl ammonium cations such as -dialkyl ammonium cation, diisopropyl ammonium cation, and dicyclohexyl ammonium cation.
  • phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenol) phosphonium cation, and tris (dimethylphenol) phosphomucation. It is done.
  • R e + a carb cation, an ammonium cation, etc. are preferable, and in particular, a tricarb cation, ⁇ , ⁇ -dimethyl arlium cation, ⁇ , ⁇ - decyl arium cation Is preferred.
  • carbamate salt examples include triphenyl carbe tetraphenol, triphenyl carve tetrakis (pentafluorophenol) borate, triphenyl carbe tetrakis (3,5- Ditrifluoromethylphenol) borate, tris (4-methylphenol) -L) carbtetrakis (pentafluorophenol) borate, tris (3,5-dimethylphenol) carbtetrakis (pentafluorophenol) borate .
  • ammonium salt examples include trialkyl-substituted ammonium salts, ⁇ , ⁇ -dialkylauryum salts, dialkylammonium salts, and the like.
  • trialkyl-substituted ammonium salts include, for example, triethyl ammonium tetraphenol, tripropyl ammonium tetraphenyl, tri ( ⁇ -butyl) ammonium tetraphenol, trimethyl ammonium.
  • ⁇ , ⁇ -dialkyl dimethylureate salts include ⁇ , ⁇ -dimethyl dimethyl-tetramethyl borate, and ⁇ , ⁇ -dimethyl dimethyl-tetrakis (pentafluorophenol) borate.
  • ⁇ , ⁇ -Dimethylaureum tetrakis (3,5-ditrifluoromethylphenol) borate, ⁇ , ⁇ -Jetylayuyltetraphenol, ⁇ , ⁇ -Jetyryarum tetrakis (pentafluorophenol) ) Borate, ⁇ , ⁇ -Jetilla Yuryum Tetrakis (3 , 5-ditrifluoromethylphenol) borate, ⁇ , ⁇ - 2,4,6-pentamethylmethyluretatetraole, ⁇ , ⁇ -2,4,6-pentamethylmethyluretatetrakis (Pentafluorofe
  • dialkyl ammonium salts include di (1-propyl) ammonium tetrakis (pentafluorophenol) borate and dicyclohexyl ammonium tetratetra
  • ionic compounds disclosed by the present applicant Japanese Patent Laid-Open No. 2004-516766 can be used without limitation.
  • the ionic compound (b-2) as described above may be used as a mixture of two or more.
  • Organoaluminum compound (also referred to as “component (b-3)” in the present specification) that forms an olefin polymerization catalyst includes, for example, an organoaluminum represented by the following general formula [7] Examples thereof include compounds and complex alkyl compounds of Group 1 metal and aluminum represented by the following general formula [8].
  • R a and R b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different from each other,
  • X represents a halogen atom,
  • m is 0 ⁇ m ⁇ 3
  • n is 0 ⁇ n ⁇ 3
  • p is 0 ⁇ p ⁇ 3
  • q is 0 ⁇ q ⁇ 3
  • m + n + p + q 3.
  • tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum;
  • Tri-branches such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum Chain alkyl aluminum;
  • Tricycloquinolenoreminium such as tricyclohexylaluminum, tricyclooctylaluminum
  • Triarylaluminums such as triphenylaluminum and tritrylaluminum
  • Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
  • Aluminum oxide such as isoprene aluminum
  • Alkylanoleminum guanoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide;
  • Dialkylaluminum alkoxides such as dimethylaluminum methoxide, jetylaluminum ethoxide, dibutylaluminum butyloxide;
  • Alkenyl oleorenoreminium sesquianolecoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
  • Alkyl aluminum aryloxides such as jetyl aluminum phenoxide, jetyl aluminum (2,6-di-t-butyl-4-methyl phenoxide);
  • Dialkylaluminum halides such as dimethylaluminum chloride, jetylaluminum chloride, dibutylaluminum chloride, jetylaluminum bromide, diisobutylaluminum chloride;
  • Alkyl aluminum sesquihalides such as cetyl aluminum sesqui-chloride, butyl aluminum sesqui-chloride, ethyl aluminum-umsesquibromide;
  • Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride;
  • Dialkylaluminum dihydrides such as jetylaluminum hydride and dibutylaluminum hydride;
  • alkylaluminum dihydrides such as ethyl aluminum dihydride and propylaluminum dihydride
  • Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylminium ethoxybromide And so on.
  • M 2 represents Li, Na, or K
  • R a represents a hydrocarbon group having a carbon number of 15 to 15, preferably 1 to 4.
  • Examples of such compounds include LiAl (C H) and LiAl (C H).
  • a compound similar to the compound represented by the above general formula [8] can also be used, for example, an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. it can.
  • organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. it can.
  • Specific examples of such compounds include (C H) A1N (C H) A1 (C
  • organoaluminum compound (b-3) trimethylaluminum and triisobutylaluminum are preferably used from the viewpoint of easy availability.
  • the catalyst component is (aI) a crosslinked meta-mouth compound represented by the general formula [1-1], and b) (b-1) an organoaluminum compound, (b-2) a compound that forms an ion pair by reacting with the bridged metaguchicene compound (a-1), and (b-3) an organoaluminum compound
  • a carrier (c) can be used as required together with at least one selected compound.
  • the carrier (c) (also referred to herein as “component (c)”) is an inorganic or organic compound and is a granular or particulate solid.
  • component (c) is an inorganic or organic compound and is a granular or particulate solid.
  • the inorganic compound porous oxides, inorganic chlorides, clays, clay minerals, or ion exchange layered composites are preferable.
  • porous oxide specifically, SiO, Al 2 O, MgO, ZrO, TiO, B 2 O, CaO,
  • Is synthetic zeolite SiO-MgO, SiO-AlO, SiO-TiO, SiO-VO, SiO-CrO
  • SiO 2 —TiO 2 —MgO or the like can be used. Of these, SiO and Z or
  • the inorganic oxide contains a small amount of NaCO, KCO, CaCO, MgCO, NaSO,
  • Such a porous oxide has different properties depending on the type and production method.
  • (c) is a particle size force of ⁇ 300 ⁇ m, preferably ⁇ 10 to 300 ⁇ m, more preferably ⁇ 20 to 200 ⁇ m, and a specific surface area of 50 to 1000 m 2 Zg, preferably 100 to It is desirable that the pore volume is in the range of 700 m 2 Zg and the pore volume is in the range of 0.3 to 3. Ocm 3 / g.
  • a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
  • inorganic halide MgCl2, MgBr, MnCl, MnBr, or the like is used.
  • the machine chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use an inorganic halide dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitating agent.
  • the clay is usually composed mainly of a clay mineral.
  • the ion-exchange layered compound is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. It is.
  • Most clay minerals are ion-exchange layered composites.
  • these clays, clay minerals, and ion-exchange layered composites are not limited to natural ones, and artificial composites can also be used.
  • clay, clay mineral or ion-exchange layered composites such as clay, clay mineral, hexagonal fine packing type, antimony type, CdCl type, Cdl type, etc.
  • clays and clay minerals examples include kaolin, bentonite, kibushi clay, gyrome clay, alofen, hysingelite, neurophyllite, unmo group, montmorillonite group, vermiculite, lyotadi stone group, norigoskite, kaori Knight, nacrite, datekite, halloysite, etc., and the ion-exchange layered composite includes: a -Zr (HAsO) ⁇ ⁇ 0, a
  • Examples include crystalline acid salts of divalent metals.
  • Such a clay, clay mineral, or ion-exchange layered composite having a pore volume of 20 or more in radius measured by mercury intrusion method is preferably 0.3 to 5 78, preferably having a pore volume of 0.178 or more. Is particularly preferred.
  • the pore volume is the mercury intrusion method using a mercury porosimeter. Is measured for a range of pore radii from 20 to 3 ⁇ 10 4 A.
  • the clay and clay mineral are preferably subjected to chemical treatment.
  • chemical treatment any of a surface treatment that adheres to the surface and removes impurities and a treatment that affects the crystal structure of clay can be used.
  • Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.
  • acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure.
  • Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.
  • salt treatment and organic matter treatment ionic complexes, molecular complexes, organic derivatives, etc. can be formed, and the surface area and interlayer distance can be changed.
  • the ion-exchangeable layered compound is a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions, utilizing the ion-exchangeability. It may be. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Also, the introduction of another substance between the layers of the layered composite is called intercalation. Intercalation guest compounds include cationic inorganic compounds such as TiCl and ZrCl, Ti (OR), Zr (OR), PO (OR), B (OR)
  • Metal alkoxides such as 4 4 4 4 3 (R is a hydrocarbon group, etc.), [Al O (OH) [Zr (OH)
  • Metal hydroxide ions such as Fe 2 O OCOCH)] + and the like. These compounds are
  • metal alkoxides such as Si (OR), Al (OR), Ge (OR) (R is carbonized).
  • Examples of the billet include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
  • montmorillonite, vermiculite, pectolite, theolite and synthetic mica are particularly preferred because clay and clay minerals are preferred.
  • the clay, clay mineral, and ion-exchange layered composite may be used as they are, or may be used after a treatment such as ball milling or sieving.
  • newly adsorbed water Or may be used after heat dehydration.
  • it can be used alone or in combination of two or more.
  • an organic aluminum oxide compound such as an alkylaluminoxane is used. It is also possible to reduce the amount of goods used.
  • the ion-exchange layered silicate is not limited to a natural product that is produced mainly as a main component of clay minerals, and may be an artificial synthetic product. Specific examples of clay, clay mineral, and ion-exchange layered silicate include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, theolite, synthetic mica, synthetic hectorite, and the like.
  • Examples of the organic compound include granular or fine-particle solids having a particle size in the range of 3 to 300 ⁇ m, preferably 10 to 300 ⁇ m.
  • (co) polymers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like having ⁇ -olefins having 2 to 14 carbon atoms as the main component, vinylcyclohexane and styrene are used.
  • a polymer or modified product having These particulate carriers can be used alone or in combination of two or more.
  • the catalyst component is (a-1) a bridged metalocene compound represented by the general formula [1], and (b) (b-1 ) An organoaluminum compound, (b-2) a compound that forms an ion pair by reacting with the above-mentioned bridged metaguchicene compound (a-1), and (b-3) an organoaluminum compound.
  • it can also contain a specific organic compound component (d) as described later, if necessary, together with one kind of compound, if necessary, the carrier (c).
  • the organic compound component improves the polymerization performance and the physical properties of the produced polymer as necessary.
  • organic compound component (d) includes, but is not limited to, alcohols, phenolic compounds, strength rubonic acid, phosphorus compounds and sulfonates.
  • Method for producing an olefin polymer using the olefin polymerization corrosion (1)
  • the usage and order of addition of each component can be arbitrarily selected. Examples of the polymerization method include the following methods.
  • component (a-1) and component (b) are added to the polymerization vessel in any order.
  • component (b) is supported. If necessary, the component (b) is supported in any order. Can be added in In this case, component (b) may be the same or different.
  • a catalyst component may be further supported on the prepolymerized solid catalyst component.
  • this olefin polymerization method provides an olefin polymer by polymerizing or copolymerizing olefin in the presence of the above-mentioned catalyst for olefin polymerization.
  • the polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method.
  • a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method.
  • the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as pentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane Alternatively, a mixture of these can be used, and the olefins to be polymerized themselves can be used as
  • (a-1) is per liter of the reaction volume, usually 10- 9 ⁇ : LO- 1 mole, preferably 10- 8 ⁇ : LO- used in an amount such that 2 moles.
  • Component (b-1) is a molar ratio of component (b-1) to all transition metal atoms (M) in component (a-1) [(bl) / M] usually 0.01. It is used in an amount of ⁇ 5000, preferably 0.05 to 2,000.
  • the component (b-2) has a molar ratio [(b-2) / M] of the component (b-2) and the transition metal atom (M) in the component (a-1) usually from 1 to 10.
  • the amount is preferably 1 to 5.
  • Component (b-3) usually has a molar ratio [(b-3) / M] of the aluminum atoms in component (b-3) to all transition metals (M) in component (a-1). It is used in an amount of 10 to 5000, preferably 20 to 2000.
  • component (d) has a molar ratio [(d) / (b-1)] of usually 0.01 to 10, preferably 0.00.
  • component (b) is component (b-2) in an amount of 1 to 5
  • the molar ratio (d) / (b-2)] is usually 0.01 to 10, preferably 0.1.
  • the component (b) is the component (b-3) in an amount such that it is ⁇ 5
  • the molar ratio [(d) / (b-3)] is usually 0.01-2, preferably 0.00. It is used in an amount such that 005 to 1.
  • the polymerization temperature of olefin using such olefin polymerization catalyst is usually 50 to
  • the polymerization pressure is usually from normal pressure to lOMPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. . It is also possible to carry out the polymerization in two or more stages with different reaction conditions.
  • the molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted by the amount of component (b) used. When adding hydrogen, the appropriate amount is about 0.001 to 100 NL per kg of olefin.
  • the olefins supplied to the polymerization reaction are one or more monomers for which an a-olefin binder having 2 or more carbon atoms is also selected.
  • ⁇ -Olefin is a linear or branched ⁇ -olefin having a carbon number of ⁇ ⁇ 20, such as ethylene, propylene, 1- Butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1- Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
  • Decene 2-methyl 1,4,5,8-dimethano-1,2,3,4,4 &, 5,8,8 &-octahydronaphthalene;
  • ⁇ , ⁇ -unsaturated such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride and bicyclo (2,2, 1) -5-heptene-2,3-dicarboxylic anhydride
  • Polar monomers such as carboxylic acids, and metal salts such as sodium, potassium, lithium, zinc, magnesium and calcium salts thereof;
  • Bull esters such as butyl acetate, propionate, caproate, force-purate, laurate, stearate, and trifluoroacetate; unsaturated glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate A glycidyl etc. can be mentioned.
  • Aromatic butyl compounds such as styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ , ⁇ -dimethylstyrene, ⁇ - ⁇ -butylstyrene, m- ⁇ -butylstyrene, ⁇ - ⁇ -butylstyrene Mono or polyalkyl styrene such as;
  • styrene derivatives such as methoxystyrene, ethoxystyrene, butyl benzoic acid, methyl butyl benzoate, vinylene benzoate acetate, hydroxystyrene, 0-chlorostyrene, ⁇ -chlorostyrene, divinylbenzene;
  • the production method of the present invention (1) is one of the monomers is also chosen a- Orefuinka of 3 to 20 carbon atoms as an example (e.g., propylene) a constitutional unit derived from 100 to 90 mole 0/0, preferably 10 0 to 91 mole 0/0, further ⁇ this preferably (excluding flop propylene) 100-96 mol 0/0, alpha Orefin C2-20 is a force one selected and the monomer 10-0 mol a constitutional unit derived from another monomer to the body 0/0, preferably be used in the production of 9-0 mole 0/0, more preferably 4-0 mole 0/0 containing polymer it can.
  • a- Orefuinka of 3 to 20 carbon atoms as an example (e.g., propylene) a constitutional unit derived from 100 to 90 mole 0/0, preferably 10 0 to 91 mole 0/0, further ⁇ this preferably (excluding flop
  • Such an ⁇ -olefin polymer preferably has a syndiotactic structure.
  • the rrrr value measured by the method described below is preferably 70% or more, and preferably 85% or more. ,.
  • the production method of the present invention (1) includes, as an example, 100 to 50 mol% of a structural unit derived from ethylene and one or more monomers selected from ⁇ -olefin linkers having 3 to 20 carbon atoms. It can be used for the production of a polymer having a constitutional unit of 50 to 0 mol%. Examples of this include the production of ethylene homopolymers.
  • the production method of the present invention (1) can of course be used for production of other polymers.
  • Crystal melting peak when a polymer sample held at 200 ° C for 10 minutes is cooled to 30 ° C, held for 5 minutes and then heated at 10 ° CZ by differential scanning calorimetry (DSC) Force is also calculated.
  • DSC differential scanning calorimetry
  • Tm One mark is written as Tm. In the case of one, it was written as Tm.
  • the stereoregularity (rrrr) also calculates the 13 C-NMR ⁇ vector measuring force. Ie
  • the rrrr fraction is expressed as Prrrr in the 13 C-NMR ⁇ vector (absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously syndiotactically bonded) and Pw (total of propylene units). From the absorption intensity of the absorption intensity derived from the methyl group, it is determined by the following formula (1).
  • NMR measurement is performed as follows, for example. That is, 0.35 g of sample is dissolved by heating in 2. Oml of hexachlorobutadiene. After filtering this solution through a glass filter (G2), add 0.5 ml of deuterated benzene and insert it into an NMR tube with an inner diameter of 10 mm. Then, 13 C-NMR measurement is performed at 120 ° C using a JEOL GX-500 type NMR measurement device. The number of integrations shall be 10,000 times or more.
  • propylene is polymerized with at least one monomer selected from ⁇ -olefin and a polyoler.
  • the crosslinked meta-mouth compound (a-2) represented by the general formula [1-2] (also referred to as “component (a-2)” in the present specification) has a chemical structure. It has the following features [m2-l] to [m2-3]. [0244] [m2-l] Of the two ligands, one is an optionally substituted cyclopentagel group, and the other is a substituted fluorenyl group (hereinafter referred to as “substituent”). , Sometimes referred to as a “substituted fluorenyl group”.
  • [0245] A covalent bridge containing two carbon atoms or a carbon atom having a aryl group or a substituted aryl group (hereinafter referred to as a covalent bond containing an aryl group or a substituted aryl group) Sometimes referred to as “cross-linking”.
  • the transition metal (M) constituting the bridged metaguchicene compound is titanium, zirconium or hafnium.
  • the cyclopentagel group may or may not be substituted.
  • Substituted ⁇ succinol pentagel group means that the cyclopentagel group moiety in the general formula [1-2] is R 2 , R 3 and R 4 are all cyclopentagel groups which are hydrogen atoms, and the substituted cyclopentagel group is: Any one or more of R 3 and R 4 may be a hydrocarbon group (f 1) or a cyclopentagel group substituted with a silicon-containing group (f 2). Further, adjacent substituents from Ri to R 4 may be bonded to each other to form a ring. When two or more of R 3 and R 4 are substituents other than a hydrogen atom, these substituents may be the same as or different from each other.
  • substituents Ri ⁇ R 4 hydrocarbon group (fl) the substituent is, to form a ring together with another substituent, Do, the case, the total number of carbon atoms from 1 to 20 Preferred examples thereof include hydrocarbon groups (hereinafter also referred to as “hydrocarbon groups (f 1 ′)”).
  • R 2 and R 3 are hydrocarbon groups (f 1)
  • R 2 and R 3 are bonded to each other to form a ring (hereinafter also referred to as "ring (f"')"). May also be mentioned.
  • the substituents R 2 and R 3 In the case of bonding to form a ring, it is more preferable that only R 2 and R 3 form a ring among Ri to R 4 .
  • R 2 when the substituents R 2 and R 3 are bonded to each other to form a ring, R 2 described above, regardless of whether each preferred carbon number is 1 to 20,
  • the total number of carbon atoms of the two substituents forming the ring is preferably 2 to 40, more preferably 3 to 30, and further preferably 4 to 20.
  • the substituents R 2 and R 3 are bonded to each other to form a ring, some of the hydrogen atoms directly bonded to the carbon of the substituent are halogen atoms, oxygen-containing groups, nitrogen
  • the total number of carbon atoms of the two substituents forming the ring may be the oxygen-containing group, nitrogen-containing group, or silicon-containing group. Include the number of carbons contained in.
  • the hydrocarbon group having 1 to 20 carbon atoms (fl ') is an alkyl group, an alkenyl group, an alkynyl group or an aryl group composed only of carbon and hydrogen.
  • hydrocarbon group having 1 to 20 carbon atoms was directly bonded to these carbons other than the alkyl group, alkenyl group, alkynyl group and aryl group composed only of carbon and hydrogen. Also included are heteroatom-containing hydrocarbon groups in which some of the hydrogen atoms are substituted with halogen atoms, oxygen-containing groups, nitrogen-containing groups, or silicon-containing groups. As such a hydrocarbon group (fl '),
  • Methyl group ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nor group, a linear hydrocarbon group such as an n-deoxy group;
  • Cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group and adamantyl group;
  • Hetero atom-containing hydrocarbon groups such as trifluorobenzobenzyl group
  • the silicon-containing group (f2) is a group having a key atom covalently bonded to the ring carbon of the cyclopentagel group, and specifically an alkylsilyl group or a arylsilyl group.
  • Preferred examples of the carbon-containing group (f2) include those having a total carbon number of 1 to 20 (f2 ') when the substituent does not form a ring with other adjacent substituents.
  • groups in which a silicon atom is substituted with three hydrocarbon groups such as a trimethylsilyl group and a triphenylsilyl group can be exemplified.
  • R 1 and R 4 are the same atom or the same group, and R 2 and R 3 are bonded to form a ring or R 2 And R 3 are preferably the same atom or the same group, more preferably R 1 and R 4 are hydrogen atoms. Particularly preferred is that all of R 2 , R 3 and R 4 are hydrogen atoms! / ,.
  • R 6 and R 11 are the same atom or the same selected hydrogen, a hydrocarbon group, a silicon-containing basic force.
  • R 7 and R 1Q are hydrogen, a hydrocarbon group, and a silicon-containing basic force, the same atom or the same group selected, and R 6 , R 7 , R 1Q and R 11 are all hydrogen atoms at the same time. It is not a child. Therefore, R 6 , RR 1Q , and R 11 may be the above-described hydrocarbon group (fl) or the above-described silicon-containing group (12).
  • R 5 , R 8 , R 9 and R 12 are each an atom or group selected from hydrogen, a hydrocarbon group (fl) and a silicon-containing group (12), which may be the same or different. Adjacent substituents from R 5 to R 12 may be bonded to each other to form a ring. [0259]
  • the substituent R 5 to R 12 hydrocarbon group used in (f 1), the substituent is, to form a ring together with another substituent, Do, the case, the total number of carbon atoms 1 Preferred is a hydrocarbon group (hydrocarbon group (f 1 ′)) of ⁇ 20.
  • R 5 to R 12 are hydrocarbon groups (fl)
  • the substituent is bonded to an adjacent substituent among R 5 to R 12 to form a ring. Also mentioned. In this case, adjacent substituents among R 5 to R 12 are bonded to each other to form a ring (ring ( ⁇ ′))! /
  • R 5 to R 12 when adjacent substituents of R 5 to R 12 are bonded to each other to form a ring (f "'), two adjacent R 5 to R 12 , 3 One or four of them may be bonded to each other to form a ring, and it is preferred that two adjacent R 5 to R 12 form a ring.
  • the total number of carbon atoms of the two substituents forming the ring is preferably 2 to 40, regardless of whether the preferred carbon number of each of R 5 to R 12 is 1 to 20 Preferably it is 3-30, and it is further more preferable that it is 4-20.
  • a part of the hydrogen atoms directly bonded to the carbon of the substituent contains a halogen atom and an oxygen-containing group. May be substituted with a group, a nitrogen-containing group, or a silicon-containing group.
  • the total number of carbon atoms of the substituents includes the number of carbon atoms contained in the oxygen-containing group, nitrogen-containing group, and silicon-containing group.
  • R 6 , RR 1Q and R 11 are all groups other than hydrogen atoms, that is, R 6 R 11 and R 11 are preferably the same group selected as the hydrocarbon group and the silicon-containing base, and R 7 and R 1Q are preferably the same group selected as the hydrocarbon group and the key-containing base.
  • hydrocarbon group If it is a hydrocarbon group and does not form a ring with an adjacent group, it is independently a hydrocarbon group having 2 or more carbon atoms, more preferably 3 or more, and particularly preferably 4 or more.
  • R 6 forms a ring with R 7 and R 11 forms a ring with R 1Q .
  • Each is a group containing silicon.
  • a key group-containing group in which the total number of carbon atoms and the number of key atoms is 3 or more, preferably 4 or more is preferable.
  • R 6 when R 6 is a hydrocarbon that does not form a ring with an adjacent group, and R 7 is a hydrocarbon group that does not form a ring with an adjacent group, , R 6 preferably has the same or more carbon number than R 7 .
  • R 6 is a key group and R 7 is a key group
  • the total number of key atoms and carbon atoms in R 6 is the total number of key atoms and carbon atoms in R 7
  • R 6 is a hydrocarbon group that does not form a ring with an adjacent group
  • R 7 is a key group
  • the number of carbon atoms in R 6 is the same as that of the carbon atom in R 7.
  • it is equal to or greater than the total number of atoms.
  • R 6 is a silicon-containing group and R 7 is a hydrocarbon group that does not form a ring
  • the total number of carbon atoms and carbon atoms in R 6 is equal to or equal to the number of carbon atoms in R 7. The above is preferable.
  • Examples of the hydrocarbon group and the silicon-containing group of R 6 , R 7 , R 10 , and R 11 include those described above.
  • the above-described hydrocarbon group (fl ') and ring ( ⁇ ') , A carbon-containing group having 1 to 20 carbon atoms (f 2 ′), etc., and the specific substituent is particularly preferably a tert-butyl group, a methyl cyclohexyl group, a methyladamantyl group, Examples thereof include a phenol group and a naphthyl group.
  • R 6 , R 7 , R 10 and R 11 are not present as independent substituents.
  • R 6 and R 7 , and R 1Q and R 11 may be bonded to each other to form a ring, and are listed as one of the most preferred forms of the substituted fluorenyl group of the bridged metallocene compound (a-2). .
  • the main chain part of the bond connecting the cyclopentagel group and the substituted fluorenyl group is a divalent covalent bond containing one carbon atom or one silicon atom.
  • the important point in the polymerization method of the present invention (2) is that the bridging atom Y of the covalent bond bridging portion may be a specific group, preferably a specific aryl group or a substituted aryl group [R 13 And R 14 ].
  • a specific group which may be the same as or different from each other, preferably a specific aryl group or a substituted aryl group is introduced into the bridging atom (Y). High-molecular-weight olefin polymers that cannot be achieved can be produced efficiently.
  • R 13 and R 14 are aryl groups having 6 to 18 carbon atoms, alkyl groups having 1 to 40 carbon atoms, alkylaryl groups having 6 to 40 carbon atoms, fluoroaryl groups having 6 to 20 carbon atoms, carbon Fluoroalkylaryl group having 7 to 40 carbon atoms, chloroaryl group having 6 to 20 carbon atoms, chloroaryl group having 7 to 40 carbon atoms, bromoaryl group having 6 to 20 carbon atoms, 7 to 7 carbon atoms 40 bromoalkyl reel groups, 6 to 20 carbon aryl groups, 7 to 40 carbon alkyl reels selected and may be the same or different and at least one of R 13 and R 14 Is an aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a bromoaryl group having 6 to 20 carbon atoms, and a 7 to 40 carbon atom group
  • Bromoalkylaryl group 6 to 20 carbon aryl group, 7 to 40 carbon atoms ® over de alkyl ⁇ or aryl group and full O b alkyl ⁇ aryl group having 7 to 40 carbon atoms, et al are selected.
  • R 13 and R are an aryl group having 6 to 18 carbon atoms, a fluoroalkylaryl group having 7 to 40 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, or an alkyl group having 7 to 40 carbon atoms.
  • R 13 and R 14 is an aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, or a black and white group having 7 to 40 carbon atoms.
  • Alkylaryl group bromoaryl group having 6 to 20 carbon atoms, bromoalkylaryl group having 7 to 40 carbon atoms, odoaryl group having 6 to 20 carbon atoms, odoalkyl aryl group having 7 to 40 carbon atoms and 7 to 40 carbon atoms Fluoroalkyl aryl base selected.
  • aryl groups or substituted aryl groups include aryl groups having 6 to 18 carbon atoms such as phenol groups, naphthyl groups, anthryl groups, and phenanthryl groups, and aromatic hydrogens (sp2 type).
  • sp2 type aromatic hydrogens
  • a group in which one or more of (hydrogen) are substituted with a substituent can be exemplified.
  • carbons such as phenyl groups such as phenyl groups, aryl groups such as naphthyl groups, carbon atoms such as naphthyl groups, biphenyl groups, anthryl groups, and phenanthryl groups.
  • a chloroaryl group having 6 to 20 carbon atoms such as an aryl group having a carbon number of 11 to 14, preferably a carbon number of 11 to 14, a chlorophenol group, a dichlorophenol group, a bromophenol group or a dibromophenol group, etc.
  • 6 to 20 carbon atoms such as bromoaryl groups, odor and jorde groups, and 6 to 20 carbon atoms such as (trichloromethyl) phenol groups, bis (trichloromethyl) phenol groups, etc. 7 to 40 carbon atoms, preferably 7 to 20 carbon atoms, a 7 to 40 carbon atoms such as an alkylaryl group, (tribromomethyl) phenol group, bis (tribromomethyl) phenol group, etc. Is a bromoalkyl aryl group having 7 to 20 carbon atoms, (Triiodomethyl) phenyl group, bis (triiodomethyl) phenyl group, etc.
  • 7 to 40 carbon atoms preferably 7 to 20 carbon atoms, alkyltriaryl group, (trifluoromethyl) phenol group
  • Fluoroalkylaryl groups having 7 to 40 carbon atoms, preferably 7 to 20 carbon atoms, such as bis (trifluoromethyl) phenol groups, etc. are preferred, and these substituents are substituted at the S meta position and the Z or para position.
  • the phenyl group is particularly preferred.
  • R 13 and R 14 are each an aryl group having 6 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, Bromoaryl group having 6 to 20 carbon atoms, bromoalkyl aryl group having 7 to 40 carbon atoms, door reel group having 6 to 20 carbon atoms, iodine alkylaryl group having 7 to 40 carbon atoms and 7 to 7 carbon atoms 40 Fluoroalkyl aryl bases may be selected and may be the same or different.
  • At least one of R 13 and R 14 is an aryl group having 11 to 18 carbon atoms, or a chloroaryl group having 6 to 20 carbon atoms.
  • chloroalkylaryl and 7 to 40 carbon fluoroalkylary Is preferable that those selected groups force.
  • R 13 and R are both powerful C 7-C 18 aryl group, C 6-C 20 chloro aryl group, C 7-C 40 open alkyl aryl group, C 6-20 Bromoaryl group, 7 to 40 carbon atom bromoalkylaryl group, 6 to 20 carbon atom aryl group, 7 to 40 carbon atom alkylaryl group and 7 to 40 carbon fluoroalkyl group It is preferable that the alkyl group is selected and may be the same or different.
  • Both R 13 and R 14 are an aryl group having 11 to 18 carbon atoms and a chloroaryl group having 6 to 20 carbon atoms.
  • Q is a halogen, a hydrocarbon group (preferably a hydrocarbon group having 1 to 10 carbon atoms), a neutral, conjugated or non-conjugated gen,
  • halogen include fluorine, chlorine, bromine and iodine.
  • hydrocarbon group examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-jetylpropyl, 1 -Ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, Examples include cyclohexyl and 1-methyl-1-cyclohexyl.
  • neutral, conjugated or non-conjugated genes with 10 or less carbon atoms include s-cis- or S-trans -'- 1,3-butadiene, S-cis- or S-trans- ? 7 4 - 1,4-diphenyl - 1,3-butadiene, s- cis - or s- trans - 4-3-methyl-1,3-Pentajen, s- cis - or S- trans -? 7 4 - 1,4-dibenzyl-1,3-butadiene, S-cis- or S-trans-7?
  • a-on ligand examples include alkoxy groups such as methoxy, tert-butoxy and phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.
  • neutral ligand capable of coordination with a lone electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, And ethers such as tilether, dioxane and 1,2-dimethoxyethane.
  • j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.
  • otamethyloctahydrodibenzofluorene refers to the structure represented by formula [10]
  • otatamethyltetrahydrodicyclopentafluorene refers to the structure represented by formula [11]
  • dibenzofluorene refers to Refers to the structure represented by formula [12].
  • the above-mentioned bridged metaguchicene compound (a-2) can be produced by referring to a known method.
  • a known production method for example, the production method described in WO04Z029062 pamphlet by the present applicant can be mentioned.
  • meta-mouth compounds can be used singly or in combination of two or more.
  • the catalyst component is: (a-2) a crosslinked meta-mouth compound represented by the general formula [1-2] (a-2), and
  • the olefin polymerization catalyst (2) includes, as a catalyst component, (a-2) a bridged metalocene compound represented by the general formula [1-2], and (b) (b-1) An organoaluminum compound, (b-2) a compound that forms an ion pair by reacting with the bridged metamouth compound (a-2), and (b-3) an organoaluminum compound.
  • the above-mentioned components which may contain the carrier (c) if necessary together with one kind of compound, can be used by being supported on the particulate carrier (c).
  • the olefin polymerization catalyst (2) may also contain the organic compound component (d) as a catalyst component, if necessary.
  • component (a-2) and component (b) are added to the polymerization vessel in any order.
  • component (a-2) and component (b) are added to the polymerization vessel in any order.
  • At least two or more of the catalyst components may be in contact with each other in advance.
  • component (b) is supported in any order, if necessary. Can be added in In this case, component (b) may be the same or different.
  • the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods.
  • liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods.
  • the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane And alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof.
  • the olefins to be polymerized themselves can also be used as a solvent.
  • (a-2) is, per liter of the reaction volume, usually 10- 9 ⁇ : LO- 1 mole, preferably 10- 8 ⁇ : LO- used in an amount such that 2 moles.
  • Component (b-1) is a molar ratio of component (b-1) to all transition metal atoms (M) in component (a-2) [(b-1) / M] force usually 0 Used in an amount of 01 to 5,000, preferably 0.05 to 2,000!
  • Component (b-2) has a molar ratio [(b-2) ZM] of the aluminum atoms in component (b-2) to all transition metals (M) in component (a-2). It is used in an amount of ⁇ 1,000, preferably 1 to 500.
  • Ingredient (b-3) is the molar ratio of (b-3) to the transition metal atom (M) in ingredient (a-2) [(b-3 ) ZM] is usually used in an amount of 1 to 10,000, preferably 1 to 5,000.
  • propylene and at least one monomer selected from a-olefin and polyoler are usually copolymerized in the liquid phase.
  • a hydrocarbon solvent is generally used, but ⁇ -olefin may be used as a solvent.
  • Copolymerization can also be carried out by batch or continuous processes.
  • Examples of ⁇ -olefins that can be used in the polymerization include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3- Examples include methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
  • Hyolefin can be used alone or in combination of two or more.
  • ⁇ -olefin and polyene as described above may be used in combination.
  • the concentration of the compound in the polymerization system is usually 0.0005 to 1 mmol per liter of the polymerization volume. Preferably it is used in an amount of 0.0001 to 0.50 mmol.
  • the reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes. Between ⁇ 1.5 hours.
  • the propylene and at least one monomer selected from ⁇ -olefin and polyene are each in an amount such that a propylene copolymer (B1) having a specific composition as described above can be obtained. To be supplied.
  • a molecular weight regulator such as hydrogen can be used.
  • the propylene-based copolymer (B1) is usually obtained as a polymer solution containing the same. .
  • This polymerization solution is treated by a conventional method to obtain a propylene-based copolymer (B1).
  • the copolymerization reaction usually has a temperature of 40 to 200 ° C, preferably 40 to 180 ° C, more preferably 50. . ⁇ 150. . In the range of 0 to 10 MPa, preferably 0.5 to: LOMpa, more preferably 0.5 to 7 MPa.
  • a propylene copolymer having a high molecular weight for example, a propylene copolymer having a high molecular weight (specifically, [7?]> 2.0)
  • the intrinsic viscosity [ ⁇ ] (measured in decalin at 135 ° C) of the propylene-based copolymer (B1) obtained by the production method of the present invention (2) is from 0.1 to: LOdlZg preferably 0.3 to From 7dlZg ⁇ Preferably it is 0.5-5 dlZg.
  • the melt flow rate (MFR; ASTM D 1238, 190. ⁇ , load 2.1613 ⁇ 4) of the propylene-based copolymer (B1) is 0.01 to 200 gZlO min, preferably ⁇ or 0.05 to LOOg / 10 min.
  • the amount is 0.05 to 80 g / 10 min, particularly preferably 0.05 to 20 g ZlO.
  • the propylene content of the propylene-based copolymer (B1) obtained from the production method of the present invention (2) is 95 to 51 mol. %, it is desirable that preferably 90-51 mole 0/0, more preferably in the range of 90 to 55 mol%.
  • the ⁇ -olefin component of the propylene-based copolymer (B1) is selected from, for example, ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. at least one is preferable instrument propylene copolymer (B1) in ⁇ that - Orefin derived configuration unit 5 to 49 mole 0/0, preferably from 10 to 49 mole 0/0, more preferably 10 to it is desirable that contained in 45 mol 0/0 range.
  • One or more ⁇ -olefin components may be contained.
  • the total content of propylene-derived structural units and ⁇ -olefin-derived structural units in the propylene-based copolymer (B1) is 100 mol%.
  • Polyene is preferably contained in the propylene-based copolymer (B1), which is preferably selected from Gen or Trien's force, within the range of the structural unit power derived from polyene to 20 mol%.
  • propylene copolymer (B1) contains a Poryen components in propylene-based interpolymer polymer (B1), propylene and at- Orefuin (excluding propylene) total 100 moles of the 0/0 (propylene-derived constituent units of Tohi - (excluding propylene) Orefin respect total 100 mole 0/0) of the constitutional unit derived from, includes an amount of 20 mole 0/0 or less than the structural unit force 0 mole 0/0 derived Poryen .
  • the gen examples include a non-conjugated gen and a conjugated gen as described above. Among these, gen having a norbornene skeleton is preferable.
  • the structural units derived from the above-mentioned gen forces may be included in one kind or two or more kinds.
  • triene examples include non-conjugated triene and conjugated triene as described above. It is. Of these, 4,8-dimethyl-1,4,8-decatriene and 4-ethylidene-8-methyl-1,7-nonadiene (EMND) are preferred!
  • the structural unit from which the above-mentioned Trienka is derived may be contained in one kind or two or more kinds.
  • the structural unit from which Torenka is derived and the structural unit from which the gen power is also derived may be included.
  • these polyen components a structural unit from which polyenka having a norbornene skeleton is derived is particularly preferable.
  • the iodine value of the propylene-based copolymer (B1) containing the above-described polyene component is usually 1 to 80, preferably 5 to 60.
  • a propylene-based copolymer containing a large amount of a-olefin having a high molecular weight and having 4 or more carbon atoms, which has been difficult to produce can be easily produced.
  • the propylene-based copolymer (B1) obtained from this for example, the molar fraction of the structural unit from which ethylenca is also derived is P, and carbon such as 1-butene or 1-otaten is used.
  • the ratio P / P is, for example, 0 to 0.80, preferably 0 to 0.6.
  • the ratio P / P is, for example, 0.05 to 0.80, preferably 0.06 to 0.60, and more preferably
  • syndiotactic propylene polymer (A) according to the present invention (3) (propylene-based polymer (A)) and the molded product having the propylene polymer strength are the best for carrying out the invention. A form is demonstrated.
  • the syndiotactic propylene polymer (A) of the present invention (3) is a propylene polymer containing a structural unit in which propylene power is also derived in an amount exceeding 90 mol% (provided that The total is 100 mol%. ).
  • the syndiotactic propylene polymer (A) of the present invention (3) has the requirements [1] and [2-1], preferably the requirements [1], [2-2] and [ 3], more preferably a propylene-based polymer having requirements [1] to [4], more preferably a propylene-based polymer satisfying requirements [a] to [d] in addition to requirements [1] to [4]
  • it may be a homopolypropylene, a propylene ' ⁇ -olefin (excluding propylene) random copolymer having 2 to 20 carbon atoms, or a propylene block copolymer.
  • ⁇ -olefin having 2 to 20 carbon atoms other than propylene includes ethylene, 1-butene, 3-methyl-1-butene, 1 pentene, 1-hexene, 4-methyl-1-pentene, 1— Otaten, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
  • the propylene polymer of the present invention (3) contains more than 90 mol% of structural units from which propylene power is also derived (however, the total amount of the structural units in the polymer (A) is 100 mol%).
  • the structural unit that also leads to propylene power exceeds 90 mol% and is less than 100 mol%
  • the structural unit that also leads to ⁇ -olefin (excluding propylene) with 2 to 20 carbon atoms includes Omol% or more and less than 10 mol%
  • a propylene polymer (provided that the total number of structural units is 100 mol%), preferably 91 to 100 mol% of structural units derived from propylene and an a-olefin having 2 to 20 carbon atoms ( (Excluding propylene) Force Propylene polymer containing structural units derived from Omol% to 9mol% (however, the total of structural units is 100mol%), more preferably structural units from which propylene power is also derived.
  • the syndiotactic propylene polymer of the present invention (3) is a propylene acrylate.
  • the structural unit from which propylene power is also derived is 94-99.9 mol%
  • the structural unit from which ⁇ -olefin (excluding propylene) having 2 to 20 carbon atoms is derived is 0. 1 to 8 mol%, preferably 93 to 99.9 mol% of structural units derived from propylene carbonate, and 0 to structural units derived from ⁇ -olefin (excluding propylene) force of 2 to 20 carbon atoms.
  • homopolypropylene is more preferable from the viewpoint of heat resistance and the like.
  • the intrinsic viscosity [r?] Of the syndiotactic propylene polymer (A) of the present invention (3) measured in decalin at 135 ° C is usually from 0.01 to LO.OOdLZg, preferably 0.10 to 9.00 dL / g, more preferably 0.50 to 8.00 dL / g, still more preferably 0.95 to 8.00 dL / g, particularly preferably 1.00 to 8.00, still more preferably 1.40 to 8.00 dL / g Even if it is desirable to be in the range, it is preferable to be in the range of 1. 40-5. OOdL / g.
  • the syndiotactic propylene polymer (A) of the present invention (3) satisfies the following requirements [1] and [2-1], preferably the following requirements [1], [2-2] and [3] It is characterized by satisfying.
  • the melting point (Tm) obtained from a differential scanning calorimeter (DSC) is 145 ° C or higher.
  • the melting point (Tm) obtained from a differential scanning calorimeter (hereinafter referred to as DSC) is 145 ° C or higher, and the heat of fusion ( ⁇ ) force is OmiZmg or higher.
  • Such a syndiotactic propylene polymer (A) is excellent in moldability, heat resistance, transparency, rigidity and tensile breaking strength when applied to molding. Below are requirements [1]-[3] Will be described in detail.
  • the syndiotactic propad polymer used in the present invention has a syndiotactic pentad fraction (rrrr fraction, pentad syndiotacticity) measured by NMR method of 85% or more, preferably 90% or more,
  • the syndiotactic propylene polymer (A) having an rrrr fraction in this range is more preferably 93% or more, and even more preferably 94% or more, and has excellent formability, heat resistance and transparency, and crystallinity.
  • the properties as polypropylene are favorable and preferable.
  • the upper limit of the rrrr fraction is not particularly limited, but is 100% or less, and usually 99% or less, for example.
  • the rrrr fraction is expressed in terms of Prrrr (absorption intensity derived from the 3rd unit methyl group at the site where 5 units of propylene units are syndiotactically bonded) in the 13 C-NMR ⁇ vector and Pw (propylene).
  • Prrrr absorption intensity derived from the 3rd unit methyl group at the site where 5 units of propylene units are syndiotactically bonded
  • Pw propylene
  • NMR measurement is performed as follows, for example. That is, 0.35 g of sample is dissolved by heating in 2. Oml of hexachlorobutadiene. After filtering this solution through a glass filter (G2), add 0.5 ml of deuterated benzene and insert it into an NMR tube with an inner diameter of 10 mm. Then, 13 C-NMR measurement is performed at 120 ° C using a JEOL GX-500 type NMR measurement device. The number of integrations shall be 10,000 times or more.
  • a syndiotactic propylene polymer having an rrrr fraction in this range is preferable because it is excellent in moldability, heat resistance and mechanical properties, and has good properties as crystalline polypropylene.
  • a syndiotactic propylene polymer having an rrrr fraction in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.
  • the melting point (Tm) of the syndiotactic propylene polymer (A) obtained by differential scanning calorimetry (DSC) measurement is 145 ° C or higher, preferably 150 ° C or higher, more preferably 155 ° C or higher. Particularly preferred is 156 ° C or higher, and the amount of heat of fusion obtained at the same time.
  • ( ⁇ ) is preferably 40 mjZmg or more, preferably 50 mJ / mg or more, more preferably 52 mJ / mg or more, and particularly preferably 55 mjZmg or more. There is no particular upper limit on Tm, but it is usually below 170 ° C, for example.
  • the differential scanning calorimetry is performed, for example, as follows. About 5 mg of sample is packed in a special aluminum pan, heated to 320 ° CZmin from 30 ° C force to 200 ° C using DSCPyrisl or DSC7 made by Perkin Elma, and held at 200 ° C for 5 minutes. Decrease the temperature from 200 ° C to 30 ° C at 10 ° CZmin, hold at 30 ° C for another 5 minutes, and then obtain the melting point (Tm) from the endothermic curve when the temperature is raised at 10 ° CZmin. When multiple peaks are detected during DSC measurement, the peak detected on the highest temperature side is defined as the melting point (Tm).
  • the syndiotactic propylene polymer (A) having a melting point (Tm) in this range is preferable in that it has excellent moldability, heat resistance and mechanical properties, and has good properties as a crystalline polypropylene.
  • a syndiotactic propylene polymer having a melting point (Tm) in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.
  • Syndiotactic propylene polymer is 1 when the isothermal crystallization temperature obtained by differential scanning calorimetry (DSC) is T and the semicrystallization time at the isothermal crystallization temperature T is 1
  • the half crystallization time (t) determined by isothermal crystallization measurement is the DSC during the isothermal crystallization process.
  • the total calorific value is defined as the area between the calorie curve and the baseline, this is the time when the calorific value reaches 50%.
  • the half crystallization time (t) is measured as follows. Sample 5mg
  • the syndiotactic propylene polymer satisfying the requirement [3] has much better moldability than the existing syndiotactic propylene polymer.
  • excellent moldability means that the time from solidification to solidification is short when molding such as injection, inflation, blow, extrusion or press. Further, such syndiotactic propylene polymer is excellent in molding cycle property, shape stability, long-term productivity and the like.
  • a syndiotactic propylene polymer satisfying the requirement [3] can be produced by setting a polymerization condition as described later using a catalyst system as described later.
  • the syndiotactic propylene polymer (A) of the present invention preferably satisfies the following requirement [4] in addition to the requirements [1] to [3].
  • the amount of n-decane soluble part of the syndiotactic propylene polymer should be 1 (wt%) or less, preferably 0.8 (wt%) or less, more preferably 0.6 (wt%) or less. desirable.
  • the amount of the n-decane soluble part is an index closely related to the blocking property of the syndiotactic propylene polymer or the molded product obtained therefrom, and usually the amount of the n-decane soluble part is small, which means that the low crystalline property is low. It means that the amount of ingredients is small. That is, the syndiotactic propylene polymer ( ⁇ ′) that also satisfies the requirement [4] has very good blocking resistance. [0383]
  • the syndiotactic propylene polymer (A) of the present invention (3), preferably the syndiotactic propylene polymer ( ⁇ ') preferably satisfies the following requirements [a] to [d].
  • the tensile elastic modulus is in the range of 500 to 2000 (MPa).
  • the tensile strength at break is 20 (MPa) or more.
  • the needle penetration temperature is 145 ° C or higher.
  • the tensile modulus of the syndiotactic propylene polymer (A) of the present invention (3), preferably the syndiotactic propylene polymer ( ⁇ ′), is in the range of 500 MPa to 2000 MPa, preferably 600 MPa to 1800 MPa, more preferably 600 MPa. The range is up to 1500MPa.
  • the tensile elastic modulus is a value measured by the following procedure.
  • a 1 mm thick press sheet is punched out using an JIS No. 3 dumbbell order bell in accordance with JIS K6301 and used as an evaluation sample.
  • For measurement for example, using an Instron tensile tester I nstonl l23, measure the tensile modulus at 23 ° C with a span interval of 30 mm and a tensile speed of 30 mmZmin, and obtain the average of the three measurements. .
  • Tensile Modulus Power Syndiotactic propylene polymer in this range is preferred because of its excellent mechanical properties and strength, and good properties as crystalline polypropylene.
  • a catalyst system as described later and setting the polymerization conditions as described later a polymer having a tensile elasticity in this range can be produced.
  • the syndiotactic propylene polymer (A) of the present invention (3) preferably the syndiotactic propylene polymer ( ⁇ ′) has a tensile breaking strength of 20 (MPa) or more, preferably 2 2 (MPa) or more. More preferably, it is 25 (MPa) or more, and more preferably 30 (MPa) or more.
  • the tensile strength at break is a value measured by the following procedure.
  • the lmm-thick press sheet is in accordance with JIS K6301 and is ordered for JIS3 dumbbells. This is punched out with a sample and used as an evaluation sample.
  • For measurement for example, using an Instron tensile tester manufactured by Instron, measure the tensile rupture strength at 23 ° C with a span interval of 30 mm and a tensile speed of 30 mmZmin, and obtain the average value of the three measurements.
  • Syndiotactic propylene polymers having a bow I tension breaking strength in this range are preferred because they are excellent in mechanical properties and strength and have good properties as crystalline polypropylene.
  • a polymer having a tensile strength at break in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.
  • the internal haze of the syndiotactic propylene polymer (A) of the present invention (3), preferably the syndiotactic propylene polymer ( ⁇ ′), is 50% or less, preferably 45% or less, more preferably 30% or less. is there.
  • Syndiotactic propylene polymer having an internal haze force in this range is preferred in that it has excellent transparency and good properties as a crystalline polypropylene.
  • a polymer having an internal haze in this range can be produced by using a catalyst system as described later and setting the polymerization conditions as described later.
  • the needle penetration temperature of the syndiotactic propylene polymer (A) of the present invention (3), preferably the syndiotactic propylene polymer ( ⁇ ′), is 145 ° C. or higher, more preferably 150 ° C. or higher.
  • the needle penetration temperature (sometimes called the soft saddle point determined by TMA measurement) can be measured as follows.
  • Syndiotactic propylene polymers with needle penetration temperatures in this range are resistant to heat. It is preferred because it has excellent properties as a crystalline polypropylene, and it has excellent heat resistance, rigidity, and material strength without losing the transparency that is characteristic of syndiotactic propylene. It is preferable in terms of good characteristics.
  • a polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.
  • the present invention (3) comprises molding the syndiotactic propylene polymer (A), preferably the syndiotactic propylene polymer ( ⁇ '), more preferably the syndiotactic propylene polymer ( ⁇ "). It is related with the molded object obtained.
  • syndiotactic polypropylene polymer ( ⁇ ) of the present invention (3) and the catalyst used for the production of the syndiotactic propylene polymer ( ⁇ ) used in the present invention (4), (5) and (6) described later (3)
  • (b-2) a compound that forms an ion pair by reacting with the cross-linked meta-inccene compound (a-3), and (b-3) at least one compound that also has an organoaluminum compound force.
  • the polymerization catalyst (cat-l) consisting of the above, or the polymerization catalyst (cat-2) in which the catalyst (cat-1) is supported on a particulate carrier, is preferably used.
  • the catalyst used for the production of the syndiotactic propylene polymer (AA) used in (6) is not limited to the catalyst.
  • R 3 and R 4 are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and R 2 and R 3 may be bonded to each other to form a ring
  • R 5 , R 6 , R 8 , R 9 , R 11, and R 12 are selected as hydrogen, hydrocarbon group, and silicon-containing forces
  • two groups of R 7 and R 10 are selected as hydrocarbon groups and silicon-containing forces that are not hydrogen atoms.
  • Each may be the same or different R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , R 9 and R and R 11 and R 12
  • the adjacent groups may be bonded to each other to form a ring.
  • R 17 and R 18 are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing group, and substituents that may be the same or different from each other are bonded to each other to form a ring. It may be formed.
  • M is Ti, Zr or Hf
  • Y is carbon
  • Q is a neutral ligand force capable of coordinating with a halogen, a hydrocarbon group, a arion ligand, and a lone electron pair. Different combinations may be chosen and j is an integer from 1 to 4.
  • the above-mentioned crosslinked meta-mouth compound (a-3) can be produced by a known method, and its production method is not particularly limited. Examples of known production methods include the production methods described in WO20 01Z27124 and WO2004Z087775 by the present applicant. Further, such a crosslinked meta-mouth compound (a-3) can be used singly or in combination of two or more.
  • the compound (b) is a compound (b-2) that forms an ion pair by reacting with the organoaluminum oxide compound (bl) and the bridged metaguchicene compound (a-3). And at least one compound selected from the organic aluminum compounds (b-3).
  • the catalyst (3) includes, as a catalyst component, (a-3) a crosslinked metacene compound represented by the general formula [1-3], and (b) (b-1) Organoaluminum compound, (b-2) the cross-linked meta A compound that reacts with the mouth cene compound (a-3) to form an ion pair, and (b-3) an organic aluminum compound force is also selected, and at least one kind of compound is selected.
  • a-3 a crosslinked metacene compound represented by the general formula [1-3]
  • (b-1) Organoaluminum compound
  • b-2) the cross-linked meta A compound that reacts with the mouth cene compound (a-3) to form an ion pair
  • an organic aluminum compound force is also selected, and at least one kind of compound is selected.
  • the above-mentioned components, which may contain c) can be used by being supported on the particulate carrier (c).
  • the catalyst (3) can contain the organic compound component (d) as a catalyst component, if necessary.
  • component (a-3) and component (b) are added to the polymerization vessel in any order.
  • At least two or more of the catalyst components may be contacted in advance.
  • component (b) is supported. If necessary, the component (b) is supported in any order. Can be added in In this case, component (b) may be the same or different.
  • the solid catalyst component in which component (a-3) is supported on component (c), and the solid catalyst component in which component (a-3) and component (b) are supported on component (c) The olefin is prepolymerized! A catalyst component may be further supported on the prepolymerized solid catalyst component.
  • the polymerization may be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. ! It can be done at any time.
  • the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane And alicyclic hydrocarbons such as xylene and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.
  • the olefins to be polymerized themselves can also be used as a solvent.
  • (a-3) is 1 liter of the reaction volume, usually 10- 9 ⁇ : LO- 1 mole, preferably 10- 8 ⁇ : LO- used in an amount such that 2 moles.
  • Component (b-1) is a molar ratio ((bl) / M) of component (b-1) to all transition metal atoms (M) in component (a-3). It is used in an amount of ⁇ 5000, preferably 0.05 to 2,000.
  • Component (b-2) has a molar ratio ((b-2) / M) of component (b-2) to transition metal atom (M) in component (a-3), usually from 1 to 10. The amount is preferably 1 to 5.
  • Component (b-3) usually has a molar ratio [(b-3) / M] of aluminum atoms in component (b-3) to all transition metals (M) in component (a-3). It is used in an amount of 10 to 5000, preferably 20 to 2000.
  • component (d) has a molar ratio [(d) / (b-1)] of usually 0.01 to 10, preferably 0.00.
  • component (b) is component (b-2) in an amount of 1 to 5
  • the molar ratio [(d) / (b-2)] is usually 0.01 to 10, preferably 0.00.
  • component (b) is component (b-3) in such an amount as 1 to 5
  • the molar ratio [(d) / (b-3)] is usually from 0.01 to 2, preferably 0. Used in such an amount that it becomes 005 ⁇ 1.
  • the polymerization temperature of olefin using such olefin polymerization catalyst is usually 50 to
  • the polymerization pressure is usually from normal pressure to lOMPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.
  • the molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. can do. Furthermore, it can be adjusted by the amount of component (b) used. When adding hydrogen, the appropriate amount is about 0.001 to 100 NL per kg of olefin.
  • the syndiotactic propylene polymer (A) obtained by the polymerization method described above may be partially graft-modified with a polar monomer.
  • polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, Examples include vinyl chloride, vinyl group-containing organic ketone compounds, and carpositimide compounds.
  • the polar monomer is particularly preferably an unsaturated carboxylic acid or a derivative thereof.
  • Examples of unsaturated carboxylic acids or derivatives thereof include unsaturated compounds having at least one carboxylic acid group, esters of a compound having a carboxylic acid group and an alkyl alcohol, and unsaturated compounds having at least one carboxylic anhydride group.
  • Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.
  • Specific examples of the compound include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocis-bicyclo [2. 2.
  • unsaturated carboxylic acids such as hept-5-en-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters, and the like.
  • specific examples of such derivatives include, for example, salt maleyl, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.
  • unsaturated carboxylic acids and Z or derivatives thereof can be used singly or in combination of two or more. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid [trademark] or acid anhydrides thereof are particularly preferably used.
  • the modified syndiotactic propylene polymer is obtained by graft polymerization of a polar monomer to the syndiotactic propylene polymer (A) as described above.
  • the polar monomer is usually 1 to: LOO parts by weight with respect to 100 parts by weight of the syndiotactic propylene polymer (A). Preferably it is used in an amount of 5-80 parts by weight.
  • This graft polymerization Is usually carried out in the presence of a radical initiator.
  • radical initiator an organic peroxide or an azo compound can be used.
  • the radical initiator can be used as it is mixed with the syndiotactic propylene polymer and the polar monomer, but can also be used by dissolving in a small amount of an organic solvent. Any organic solvent that can dissolve the radical initiator can be used without particular limitation.
  • a reducing substance may be used.
  • the graft amount of the polar monomer can be improved.
  • Graft modification of the syndiotactic propylene polymer (A) with a polar monomer can be performed by a conventionally known method.
  • the syndiotactic propylene polymer (A) is dissolved in an organic solvent and then polar Adding monomer and radical initiator to the solution and reacting at a temperature of 70 to 200 ° C, preferably 80 to 190 ° C, for 0.5 to 15 hours, preferably 1 to 10 hours it can.
  • a modified syndiotactic propylene polymer can also be produced by reacting the syndiotactic propylene polymer (A) with a polar monomer in the absence of a solvent using an extruder or the like. This reaction is preferably carried out usually at a temperature equal to or higher than the melting point of the ethylene polymer, specifically at a temperature of 120 to 250 ° C., usually for 0.5 to 10 minutes.
  • modification amount of the thus modified is obtained by Shinji O tactic propylene polymer (grafted amount of the polar mode Nomar) is usually from 0.1 to 50 weight 0/0, preferably from 0.2 to 30 weight 0 / It is 0 , more preferably 0.2 to 10% by weight.
  • the above-mentioned modified syndiotactic propylene polymer is contained in the syndiotactic propylene polymer (A) of the present invention (3), it has excellent adhesion and compatibility with other resins, and the surface of the molded body is excellent. The wettability may be improved.
  • modified syndiotactic propylene polymer of the present invention (3) may be suitably used for crosslinked electric wires and crosslinked pipes by crosslinking.
  • the syndiotactic propylene polymer (A) of the present invention (3) has low moldability.
  • a nucleating agent which is a specific optional component may be blended.
  • the nucleating agent is dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di- tert-Butylphenol) Sodium phosphate, pimelic acid and its salts, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, etc.
  • the amount is preferably about 0.1 to 1 part by weight with respect to parts by weight.
  • the blending timing there is no particular limitation on the blending timing, and it can be added during polymerization, after polymerization, or during molding.
  • the syndiotactic propylene polymer (A) of the present invention (3) includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an antiblocking agent, and the like within a range not impairing the object of the invention.
  • the syndiotactic propylene polymer (A) is a method in which each component is subjected to various known methods within the above-described range, for example, a multistage polymerization in a continuous or batch manner using a slurry phase, a solution phase or a gas phase. , Henschel mixer, V-blender, riboblender, tumbler blender, etc., or after mixing, melt-kneaded with a single screw extruder, twin screw extruder, kneader, vannori mixer, etc., then granulated or pulverized It can be manufactured by adopting the method.
  • composition containing the propylene polymer (A) of the present invention is not particularly limited as long as it contains (A).
  • syndiotactic propylene polymer (A) obtained by the above method, or a modified product thereof, is excellent in moldability and heat resistance, and excellent in moldability, heat resistance, transparency, rigidity, and tensile strength. Since it is possible to obtain a molded product, it has been difficult to use syndiotactic polypropylene in the past, and it can be widely used for polyolefin applications, but in particular, syndiotactic propylene polymer (A) is Sheets, unstretched or stretched films, filaments, and other various shapes can be used. wear.
  • a molded product using the syndiotactic propylene polymer (A) is sufficient if the syndiotactic propylene polymer (A) is contained in a part of the molded product. It is better if the tick propylene polymer (A) is used.
  • the syndiotactic propylene polymer (A) may be used for the entire molded body.
  • a syndiotactic propylene polymer (A) is used as a part of the molded body, and an example thereof is a multilayer laminate.
  • the multilayer laminate is a laminate in which at least one layer is a layer containing the syndiotactic propylene polymer (A), and is a multilayer film and sheet, multilayer container, multilayer tube, aqueous system.
  • A syndiotactic propylene polymer
  • examples thereof include a multilayer coating film laminate contained as a constituent component of a paint.
  • the syndiotactic propylene polymer (A) of the present invention (3) is extrusion molding, injection molding, inflation molding, extrusion lamination molding, cast molding, blow molding, extrusion blow molding, ejection blow molding, press molding. Further, it can be formed by a known thermoforming method such as vacuum forming, calender forming, foam forming, powder slush forming or the like. Furthermore, it can be used for fibers, monofilaments, non-woven fabrics and the like.
  • These molded products include molded products (laminates and the like) including a portion made of the syndiotactic propylene polymer (A) and a portion made of other resin.
  • the syndiotactic propylene polymer (A) may be cross-linked during the molding process!
  • the molded body include extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding, powder slush molding, and the like. And a molded body obtained by the thermoforming method.
  • the molded body will be described with several examples.
  • the shape and product type are not particularly limited.
  • a sheet skin material
  • a film film
  • a tube tube
  • a catheter catheter
  • a monofilament nonwoven fabric
  • the syndiotactic propylene polymer (A) obtained by the above method, or a modified product thereof, has transparency, impact resistance, heat resistance, flexibility or rigidity, wear resistance, surface hardness, shrinkage. , Soundproofing, vibration control, cutability, high breakdown voltage, radiation resistance, dedara resistance, uniform foaming Since it is excellent in rubber elasticity, kink resistance, stretchability, creep properties, adhesiveness, softness-modifying property, transparency-modifying property, etc., it can be suitably used for the following applications.
  • a conventionally known extrusion apparatus and molding conditions can be employed.
  • the melted propylene composition can be formed into a desired shape by force-extruding a specific die using a gear extruder or the like.
  • the stretched film is obtained by using the above-described extruded sheet or extruded film (unstretched), for example, a known stretching method such as a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method, or the like. Can be obtained by stretching.
  • a known stretching method such as a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method, or the like.
  • the stretching ratio at the time of stretching the sheet or the unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 ⁇ m by stretching.
  • Inflation films can also be produced as film-like molded articles. Drawdown is unlikely to occur during injection molding.
  • Sheets and film molded articles using the syndiotactic propylene polymer (A) have mechanical properties that are difficult to be charged, heat resistance, stretchability, impact resistance, aging resistance, transparency, transparency, It is excellent in gloss, rigidity, moisture proofing and gas nourishment, and can be used widely as a packaging film.
  • the sheet and film molded body using the syndiotactic propylene polymer (A) may be a multilayer molded body, and may contain at least one layer of syndiotactic propylene polymer. Used as a multi-layer laminate.
  • the filament molded body is, for example, a molten syndiotactic propylene polymer.
  • (A) can be produced by extrusion through a spinneret. Specifically, a spun bond method and a melt bron method are preferably used. The filament thus obtained may be further stretched. This stretching should be performed to such an extent that at least one uniaxial direction of the filament is molecularly oriented.
  • the injection-molded article can be produced by injection-molding the syndiotactic propylene polymer (A) into various shapes using a known injection-molding apparatus under known conditions.
  • the injection molded body using the propylene composition has excellent transparency, rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc. It can be used in a wide range of applications such as automotive exterior materials, household appliance housings and containers.
  • the blow molded product can be produced by blow molding the syndiotactic propylene polymer (A) using a known blow molding apparatus under known conditions.
  • the blow molded article made of the syndiotactic propylene polymer (A) contains at least one layer of syndiotactic propylene polymer (A) which may be a multilayer molded article.
  • a syndiotactic propylene polymer (A) is extruded from a die in a molten state at a resin temperature of 100 ° C to 300 ° C to form a tubular parison, and then Norison. Is held in a mold having a desired shape, air is blown, and a hollow molded body can be produced by wearing the mold at a resin temperature of 130 ° C to 300 ° C. Stretching (blowing) The magnification is preferably about 1.5 to 5 times in the transverse direction.
  • the syndiotactic propylene polymer (A) is injected into a parison mold at a resin temperature of 100 ° C to 300 ° C to form a parison, and then the parison is formed in a desired shape.
  • a hollow molded body can be manufactured by blowing air after being held in a metal mold and mounting the mold at a resin temperature of 120 ° C to 300 ° C.
  • the draw (blow) magnification is preferably 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.5 times in the transverse direction.
  • the blow molded article using the syndiotactic propylene polymer (A) has excellent transparency, rigidity or flexibility, heat resistance and impact resistance, and also moisture resistance.
  • Examples of the press-molded body include a mold stamping molded body.
  • the base material when the base material and the skin material are press-molded at the same time and both are integrally formed (mold stamping molding). It can be formed of a tactic propylene polymer.
  • mold stamping molded body examples include automotive interior materials such as a door trim, a rear package trim, a seat back gash, and an instrument panel.
  • the press-molded body using the syndiotactic propylene polymer (A) is hardly charged and has rigidity or flexibility, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, Excellent wear resistance.
  • the foamed molded article using the syndiotactic propylene polymer (A) is obtained at a high expansion ratio, has good injection moldability, and has high rigidity and material strength.
  • the syndiotactic propylene polymer (A) can produce vacuum molded bodies such as interior skin materials such as automobile instrument panels and door trims.
  • the molded body is excellent in flexibility to be easily charged, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, wear resistance, and the like.
  • examples of the molded article of the present invention (3) include a laminate having at least one layer composed of the syndiotactic propylene polymer (A).
  • the propylene-based polymer of the present invention (3) is particularly an extruded product (film, sheet, etc.), Suitable for inflation molded products, injection molded products, blow molded products, and fibers, and particularly suitable for extrusion molded products, inflation molded products, injection molded products, and blow molded products from the viewpoint of transparency and heat resistance.
  • the propylene polymer of the present invention (3) is suitable for, for example, a container or a nonwoven fabric.
  • the container include a frozen storage container, a food container such as a retort bouch, and a bottle container.
  • a medical container, an infusion bag, etc. can be illustrated.
  • composition containing the propylene polymer (A) of the present invention (3) is excellent in moldability and heat resistance, it is also used for the above-mentioned uses (uses of the propylene polymer (A)). It is possible.
  • the propylene-based polymer composition (XI) of the present invention contains a specific (AA) syndiotactic propylene polymer and a specific (B2) propylene' ⁇ -olefin copolymer. It is.
  • the syndiotactic propylene polymer ( ⁇ ) used in the present invention (4) and the present inventions (5) and (6) to be described later has the following characteristics.
  • 'Alpha-olefin having 2 to 20 carbon atoms (excluding propylene) random copolymer or propylene block copolymer may be used, but preferably homopropylene or propylene-carbon atoms 2 to 20 ⁇ -olefin random copolymers.
  • homopolypropylene a copolymer of propylene and ethylene or ⁇ -olefin having 4 to 10 carbon atoms
  • a copolymer of propylene, ethylene and a-olefin having 4 to 10 carbon atoms are particularly good for its heat resistance.
  • ⁇ -olefin having 2 to 20 carbon atoms other than propylene includes ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl -1 -Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
  • the structural unit from which propylene power is derived is carbon.
  • the syndiotactic propylene polymer (AA) of the present invention usually has a propylene-derived constituent unit in an amount of more than 90 mol% and not more than 100 mol%, and an ⁇ -olefin having 2 to 20 carbon atoms.
  • syndiotactic propylene polymer (AA) is a propylene 'a -olefin random copolymer
  • a structural unit derived from ⁇ -olefin (excluding propylene) having 2 to 20 carbon atoms in an amount of 0.3 to 7 mol%, preferably 0.3 to 6 mol 0/0, further rather preferably is in an amount of 0.3 to 5 mole 0/0! / is Rukoto I like it!
  • the syndiotactic propylene polymer ( ⁇ ) has a syndiotactic pentad fraction (rrrr fraction, pentad syndiotacticity) measured by NMR method of 85% or more, preferably 90%.
  • the syndiotactic propylene polymer (AA) having an rrrr fraction in this range is excellent in moldability, heat resistance and transparency, more preferably 93% or more, and still more preferably 94% or more. From the viewpoint of good properties as crystalline polypropylene.
  • the upper limit of the rrrr fraction is not particularly limited but is 100% or less, and usually 99% or less, for example.
  • This syndiotactic pentad fraction (rrrr fraction) is measured as follows.
  • the rrrr fraction is expressed in terms of Prrrr in the 13 C-NMR ⁇ vector (absorption intensity derived from the 3rd unit methyl group at the site where 5 units of propylene units are continuously syndiotactically bonded) and Pw (propylene
  • the absorption intensity of the unit is determined by the following formula (1).
  • rrrr fraction (%) 100 X Prrrr / Pw ⁇ ⁇ ⁇ (!)
  • NMR measurement is performed as follows, for example. That is, 0.35 g of sample is dissolved by heating in 2. Oml of hexachlorobutadiene. After filtering this solution through a glass filter (G2), add 0.5 ml of deuterated benzene and insert it into an NMR tube with an inner diameter of 10 mm. Then, 13 C-NMR measurement is performed at 120 ° C using a JEOL GX-500 type NMR measurement device. The number of integrations shall be 10,000 times or more.
  • the intrinsic viscosity [7?] Of syndiotactic propylene polymer (AA) measured in decalin at 135 ° C is from 0.1 to: L0dL / g, preferably from 0.5 to LOdL / g. It is desirable to be. More preferably 0.50 to 8.00 dL / g, even more preferably 0.95 to 8.00 dL / g, particularly preferably 1.00-8.00, even more preferably 1.40 to 8.00 dL / g. In particular, it is preferably in the range of 1.40-5. OOdLZg. Syndiotactic propylene polymer (AA) with such an intrinsic viscosity [7?] Value exhibits good fluidity and is easily blended with other components and has excellent mechanical strength from the resulting composition. There is a tendency to obtain molded products.
  • the melting point (Tm) of the syndiotactic propylene polymer (AA) obtained by differential scanning calorimetry (DSC) measurement is 145 ° C or higher, preferably 147 ° C or higher. It is preferably 150 ° C or higher, more preferably 155 ° C or higher, and particularly preferably 156 ° C or higher.
  • the upper limit of Tm is not particularly limited, but is usually 170 ° C or lower, for example.
  • the heat of fusion ( ⁇ ⁇ ) of the syntactic propylene polymer (AA) obtained by differential scanning calorimetry (DSC) measurement is 40 mjZmg or more, preferably 45 mJ / mg or more, more preferably 50 mJ / mg. Above, more preferably 52 mJ / mg or more, particularly preferably 55 mjZmg or more.
  • the differential scanning calorimeter measurement is performed, for example, as follows. About 5.00 mg of sample is packed in a dedicated aluminum pan, heated to 320 ° CZmin up to 30 ° C and 200 ° C using DSCPyrisl or DSC7 manufactured by Perkin Elma Co., and held at 200 ° C for 5 minutes. Decrease the temperature from 200 ° C to 30 ° C at 10 ° C / min, hold at 30 ° C for another 5 minutes, and then from the endothermic curve when raising the temperature at 10 ° C / min, melting point (Tm) and melting Calculate the amount of heat ( ⁇ H). When multiple peaks are detected during DSC measurement, the peak detected on the highest temperature side is defined as the melting point (Tm).
  • a syndiotactic propylene polymer (AA) having a melting point (Tm) in this range is excellent in moldability, heat resistance and mechanical properties, and has good properties as crystalline polypropylene.
  • a syndiotactic propylene polymer (AA) having a melting point (Tm) in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.
  • the half-crystallization time (t) determined by isothermal crystallization measurement is the DSC during the isothermal crystallization process.
  • the syndiotactic propylene polymer (AA) satisfying the above (Eq-1) has remarkably superior moldability compared to existing ones.
  • excellent moldability means that when molding such as injection, inflation, blowing, extrusion or pressing, the time from solidification to solidification is short.
  • syndiotactic propylene polymer (AA) is excellent in molding cycle property, shape stability, long-term productivity and the like.
  • a syndiotactic propylene polymer (AA) satisfying the above (Eq-1) can be produced by setting a polymerization condition as described later using a catalyst system as described later.
  • the syndiotactic propylene polymer (AA) preferably has the following requirements in addition to the above preferred embodiments (meeting AH ⁇ 40 mjZmg and satisfying (Eq-1)) (n A mode in which the amount of the decane soluble part) is simultaneously satisfied is mentioned.
  • Syndiotactic propylene polymer (AA) n-decane soluble part amount power 1 (wt%) or less, preferably 0.8 (wt%) or less, more preferably 0.6 (wt%) or less It is desirable to be.
  • the amount of n-decane soluble part is an index closely related to the blocking characteristics of syndiotactic propylene polymer (AA) or a molded product obtained therefrom. It means that the amount of ingredients is small. That is, the syndiotactic propylene polymer (AA) satisfying this requirement (the amount of n-decane soluble part) has extremely good anti-blocking properties.
  • one of the most preferred embodiments of the component (AA) contains a syndiotactic pentad fraction (as measured by 13 C-NMR) that contains a structural unit that also leads to propylene power in an amount exceeding 90 mol%.
  • rrrr fraction is 85% or more
  • melting point (Tm) force determined by DSC is ° C or more
  • heat of fusion ( ⁇ ⁇ ) is 40 mjZmg or more
  • (Eq-1) is satisfied
  • the organoaluminum compound (b-3) is the organoaluminum compound (b-3)
  • At least one of the compounds (b), the force of which is also selected
  • the powerful polymerization catalyst (cat-l) or the polymerization catalyst (cat-2) in which the catalyst (cat-1) is supported on a particulate carrier is preferably used.
  • the catalyst used for the production of the syndiotactic polypropylene polymer (AA) is not limited to the catalyst.
  • the component (a-3), the component (b-1), the component (b-2) and the component (b-3) are supported on the particulate carrier (c) as necessary. It can also be used.
  • the olefin polymerization catalyst (3) used for the production of the syndiotactic propylene polymer (AA) may contain the organic compound component (d) as necessary together with the above components. it can.
  • component (a-3) and component (b) are added to the polymerization vessel in any order.
  • the solid catalyst component in which the component (a-3) is supported on the component (c), and the solid catalyst component in which the component (a-3) and the component (b) are supported on the component (c) The olefin is prepolymerized!
  • a catalyst component may be further supported on the prepolymerized solid catalyst component.
  • the syndiotactic propylene polymer (AA) is at least selected from propylene and ⁇ -olefin (excluding propylene) force having 2 to 20 carbon atoms in the presence of the above-mentioned catalyst for olefin polymerization. It can be obtained by polymerizing or copolymerizing one kind of olefin.
  • the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods.
  • the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, Examples include cycloaliphatic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. It is also possible to use olefin itself as a solvent.
  • Component (b-1) is a molar ratio [(bl) / M] force of component (b-1) to all transition metal atoms (M) in component (a-3), usually 0.01. It is used in an amount of ⁇ 5000, preferably 0.05 to 2,000!
  • Component (b-2) is a molar ratio of component (b-2) to transition metal atom (M) in component (a-3) [(b-2) ZM] 1S usually 1 to 10, preferably It is used in such an amount that it becomes 1-5.
  • Component (b-3) is a molar ratio of aluminum atoms in component (b-3) to all transition metals (M) in component (a-3) [(b-3) ZM] 1S It is used in an amount of ⁇ 5000, preferably 20 ⁇ 2000.
  • Component (d) has a molar ratio [(d) Z (bl)] of usually 0.01 when component (b) is component (b-1).
  • component (b) is component (b-2) in an amount such that it is ⁇ 10, preferably 0.1 to 5, the molar ratio [(d) Z (b-2)] is usually 0.01.
  • component (b) is component (b-3) in an amount of ⁇ 10, preferably 0.1 to 5, the molar ratio [(d) Z (b-3)] is usually 0. .01-2, preferably used in an amount of 0.005-1.
  • the polymerization temperature of olefin using such an olefin polymerization catalyst is usually 50 to
  • the polymerization pressure is usually from normal pressure to lOMPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. It is also possible to carry out the polymerization in two or more stages with different reaction conditions.
  • the molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted by the amount of component (b) used. When adding hydrogen, the appropriate amount is about 0.001 to 100 NL per kg of olefin.
  • the olefins supplied to the polymerization reaction are propylene and one or more olefins having an ⁇ -olefin having 2 to 20 carbon atoms (excluding propylene).
  • ⁇ -olefin having 4 to 20 carbon atoms linear or branched ⁇ -olefin having 4 to 20, preferably 4 to 10 carbon atoms, such as 1-butene, 2-butene, 1- Pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene 1-hexadecene, 1-octadecene, 1-eicosene, etc.
  • Propylene 'alpha - Orefin copolymer (B2) is a structural unit derived from propylene in amounts of 55 to 90 mole 0/0, the carbon atoms 2 to 20 alpha - Orefin (excluding propylene) or al chosen propylene 'alpha at least one structural unit Orefuinka also guided in an amount of 10 to 45 mole 0/0 is - a Orefin copolymer, in conformity with JIS ⁇ - 6721 23 0 ° C, 2.16
  • the MFR measured with a kg load is in the range from 0.01 to LOOgZ, and satisfies one or more of the following requirements (b-1) and (b-2).
  • (b-1) Syndiotactic triad fraction (rr) measured by 13 C-NMR method is 60% or more.
  • Propylene 'alpha - Orefin copolymer (B2) the amount of 55 to 95 mole 0/0 constitutional units derived from propylene, alpha C2-20 - (excluding propylene) Orefin force led Ru configuration
  • the unit contains an amount of 10 to 45 mol%.
  • the syndiotactic propylene polymer ( ⁇ ⁇ ) is 50 parts by weight or more with respect to 100 parts by weight of the total of ( ⁇ ) and ( ⁇ 2).
  • for propylene force also the amount of the constituent units 55 to 90 mole 0/0 derived, preferably 55 to 85 mole 0/0 of the amount, the more favorable Mashiku 60-85 mole 0/0 of the amount, number of carbon atoms 2-20 of alpha - (excluding propylene) Orefin 10 to 45 mol of constituent units forces also led 0/0, preferably 15 to 45 mole 0/0, the amount of more preferably 1 5 to 40 mole 0/0 contains.
  • the propylene ' ⁇ -olefin copolymer ( ⁇ 2) is a syndiotactic propylene polymer ( ⁇ ) with a total of ( ⁇ ) and ( ⁇ 2). If less than 50 parts by weight per part by weight of propylene mosquito ⁇ et amount of the constituent units 55 to 90 mole 0/0 derived, preferably in an amount of 65 to 85 Monore 0/0, more preferably 70 to 85 Monore 0/0 of the amount, further charcoal atom number 2 to 20 alpha - Orefin (excluding propylene) one or more also reduces the forces directed a structural unit 10-45 mole 0/0, preferably 15 to 35 mol the amount of 0/0, and more preferably contains an amount of 15 to 30 mol%.
  • the total of structural units derived from propylene and structural units derived from ⁇ -olefin (excluding propylene) force having 2 to 20 carbon atoms is 100 mol%.
  • ⁇ -olefins having 2 to 20 carbon atoms include ethylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl- Examples include 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Particularly preferred are ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
  • propylene' ⁇ -olefin copolymers ( ⁇ 2) as described above, propylene' An ethylene copolymer is preferred and is one of the embodiments.
  • propylene'ethylene copolymers and propylene / ethylene / HAO copolymers which are polymers in these preferred ranges, are not included in (b-1) and (b-2)! It is preferable to satisfy.
  • the propylene / ⁇ -olefin copolymer (B2) has an MFR measured at 230 ° C and 2.16 kg load in accordance with JIS 6-6721, ranging from 0.01 to L00g / 10 min. It is preferable to be in the range of 0.02 to: L00 g / 10 min.
  • the propylene' ⁇ -olefin copolymer (B2) satisfies at least one of the following (b-1) and (b-2).
  • (b-1) Syndiotactic triad fraction of propylene ' ⁇ -olefin copolymer (B2) measured by 13 C-NMR method (rr fraction, triatodosyndiotacticity) 60
  • the propylene ' ⁇ -olefin copolymer (B2) is in phase with the syndiotactic propylene polymer ( ⁇ ). Good tolerance and good! / ⁇ .
  • a polymer satisfying (b-1) can be obtained, for example, by copolymerizing propylene and ⁇ -olefin in the presence of a catalyst capable of producing syndiotactic polypropylene. For example, it may be produced using a catalyst as described later.
  • the rr fraction is expressed as Prr in the 13 C-NMR ⁇ vector (absorption intensity derived from the methyl group of the second unit at the site where 3 units of propylene units are continuously syndiotactically bonded) and Pw (propylene
  • the absorption intensity of the unit is determined by the following formula (2).
  • mr-derived absorption (absorption derived from at least both syndiotactic and lysotactic bonds out of 3 propylene units, used to determine Pmr (absorption intensity))
  • rr-derived absorption (Used to determine the absorption of Prr (absorption intensity) from the second unit methyl group at the site where three consecutive propylene units are syndiotactically bonded) or Absorption derived from mm (the propylene unit is When the absorption derived from the methyl group of the second unit, the Pmm (absorption intensity), at the site where three units are consecutively isotactically bonded, and the absorption derived from the comonomer overlap The calculation is made without subtracting the contribution of the comonomer component.
  • the value obtained according to the method for obtaining the “syndiotacticity parameter (SP value)” described up to [0031] is 60% or more, preferably 65% or more, more preferably 70% or more. It is more preferable that In other words, the rr value is mr in the calculation of the rr value.
  • Absorption derived from (used to determine at least Pmr (absorptive strength) from 3 syndiotactic and isotactic bonds out of 3 propylene units), Absorbed from rr (3 units of propylene units) Absorption derived from the second unit methyl group at the site of continuous syndiotactic bonding, used for determination of Prr (absorption intensity)), or mm-derived absorption (3 units of propylene units in succession) Absorption derived from the second unit methyl group at the site of the isotactic bond, used to determine Pmm (absorption intensity) If the strength) and absorption derived from the comonomer overlap, the contribution of the comonomer component is subtracted.
  • the NMR measurement is performed, for example, as follows.
  • (b-2) The propylene ' ⁇ -olefin copolymer (B2) is based on the intrinsic viscosity [ ⁇ ] (dL / g)] IS K-6721 measured in 135 ° C decalin. MFR (gZlO component) measured at 230 ° C and 2.16kg load satisfies the following relational expression.
  • Propylene ⁇ -olefin copolymers ( ⁇ 2) satisfying this relation are preferred because they have good compatibility with syndiotactic propylene polymers ( ⁇ ).
  • the propylene' ⁇ -olefin copolymer ( ⁇ 2) satisfying the above formula can be obtained by copolymerizing propylene and a-olefin with a catalyst capable of producing syndiotactic polypropylene, for example, as described below. It may be produced using a simple catalyst. Such materials are preferred because of their good compatibility with syndiotactic propylene polymer (AA).
  • the propylene 'a -olefin copolymer satisfying (b-2) has the same [7?] And a large MFR as compared with the conventional lysotactic propylene copolymer.
  • propylene • a-olefin copolymer is propylene having a isotactic structure It is a polymer having a stereoregularity different from an ⁇ -olefin copolymer, and is considered to have a syndiotactic structure. For this reason, the propylene ⁇ -olefin copolymer ( ⁇ 2) is considered to have good compatibility with the component ( ⁇ ).
  • This propylene 'a -olefin copolymer (B2) has a crystallinity measured by X-ray diffraction of preferably 20% or less, more preferably 0 to 15%.
  • This propylene 'a -olefin copolymer (B2) has a single glass transition temperature, and the glass transition temperature (Tg) obtained by differential scanning calorimetry (DSC) measurement is usually 0. It is preferable that the temperature is not higher than ° C. When the glass transition temperature (Tg) of the propylene ′ ⁇ -olefin copolymer (B2) is within the above range, the cold resistance and the low temperature characteristics are excellent.
  • the differential scanning calorimetry is performed, for example, as follows. Sample lO.OOmg is packed in a special aluminum pan, and the temperature is raised from 30 ° C to 200 ° C at 200 ° C Zmin using Seiko Instruments' DSCRDC220, and held at 200 ° C for 5 minutes. Decrease the temperature from 200 ° C to 100 ° C at 10 ° C Zmin, hold at 100 ° C for another 5 minutes, and then determine the glass transition temperature (Tg) from the endothermic curve when the temperature is raised at 10 ° C Zmin. Ask.
  • the molecular weight distribution (MwZMn, converted to polystyrene, Mw: weight average molecular weight, Mn: number average molecular weight) of this propylene' ⁇ -olefin copolymer (B2) measured by GPC is preferably 3.5. Below, more preferably 3.0 or less, and still more preferably 2.5 or less.
  • the organoaluminum compound (b-l) (b-l)
  • the organoaluminum compound (b-3) And at least one compound (b) selected from
  • It can be produced by polymerizing propylene and at least one olefin selected from ⁇ -olefins (excluding propylene) having 2 to 20 carbon atoms in the presence of a powerful olefin polymerization catalyst.
  • the production method is not limited to this as long as the requirements as the propylene ' ⁇ -olefin copolymer ( ⁇ 2) are satisfied.
  • R 5 , R 8 , R 9 and R 12 are a hydrogen atom, a hydrocarbon group, and a silicon-containing basic force, and each may be the same or different.
  • R 6 and R 11 are the same atom or the same group selected as a hydrogen atom, a hydrocarbon group, and a silicon-containing basic force,
  • R 7 and R 1Q are the same atom or the same group selected as a hydrogen atom, a hydrocarbon group, and a silicon-containing basic force,
  • R 1q and R 11 are not all hydrogen atoms at the same time
  • R 2 and R 3 may be bonded to each other to form a ring.
  • Adjacent groups among R 5 to R 12 may be bonded to each other to form a ring.
  • R 13 and R 14 are aryl groups having 6 to 18 carbon atoms, alkyl groups having 1 to 40 carbon atoms, alkylaryl groups having 6 to 40 carbon atoms, fluoroaryl groups having 6 to 20 carbon atoms, carbon numbers 7 to 40 fluoroalkylaryl group, 6 to 20 carbon chloroaryl group, 7 to 40 carbon chloro alkenoreanoleno group, 6 to 20 bromo aryleno group, 7 to 7 carbon atoms 40 Bromo noreki Luaryl group, 6 to 20 carbon aryl group, 7 to 40 carbon alkyl aryl group selected, which may be the same or different
  • At least one of R 13 and R 14 is an aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or a bromoaryl having 6 to 20 carbon atoms.
  • M is Ti, Zr or Hf
  • Y is carbon or silicon
  • Q is selected from the same or different combinations of halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated gen, anion ligand and neutral ligand capable of coordinating with a lone pair.
  • j is an integer of 1 to 4.
  • bridged meta-mouth compound (a-2) include the above-mentioned bridged meta-mouth compound (a-2a) described in the description of the present invention (2).
  • the above-mentioned bridged metaguchicene compound (a-2) can be produced by referring to a known method.
  • a known production method for example, the production method described in WO04Z029062 pamphlet by the present applicant can be mentioned.
  • meta-mouth compounds as described above can be used singly or in combination of two or more.
  • the organoaluminum oxide compound (b-1) used in the production of the propylene' ⁇ -olefin copolymer (B2) is an organoaluminum used in the production of the syndiotactic propylene polymer (AA).
  • the same compound as the oxy compound (b-1) is used.

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Abstract

L’invention décrit un catalyseur pour la polymérisation d'oléfine composé d’un composé métallocène réticulé (A-1) représenté par la formule générale [1-1] ci-dessous et d’au moins un ou plusieurs composés (b) choisis parmi des composés organooxyaluminium (b-1), des composés (b-2) formant une paire d'ions, et des composés organoaluminium (b-3). [1-1] (dans la formule générale [1-1], R1, R2, R3, R4, R5, R8, R9 et R12 représentent respectivement un élément choisi parmi un atome d'hydrogène, un groupe hydrocarboné et un groupe contenant un atome de silicium ; R6, R7, R10 et R11 ne sont pas des atomes d'hydrogène et représentent respectivement un élément choisi parmi un groupe hydrocarboné et un groupe contenant un atome de silicium ; R13 et R14 représentent respectivement un atome d'hydrogène, un groupe hydrocarboné autre qu'un groupe méthyle ou analogues ; M représente Ti, Zr ou analogues ; Y représente un atome de carbone ou analogues ; Q représente un atome d’halogène ou analogues ; et j représente un nombre entier de 1 à 4.)
PCT/JP2006/309972 2005-05-18 2006-05-18 Catalyseur pour la polymerisation d'olefine, procede de production d’une polyolefine, procede de production d’un copolymere de propylene, polypropylene, composition de polypropylene, et leur utilisation WO2006123759A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN2006800170896A CN101189269B (zh) 2005-05-18 2006-05-18 烯烃聚合用催化剂、烯烃聚合物的制造方法、丙烯系共聚物的制造方法、丙烯聚合物、丙烯系聚合物组合物及其用途
KR1020117007628A KR101187539B1 (ko) 2005-05-18 2006-05-18 올레핀 중합용 촉매, 올레핀 중합체의 제조방법, 프로필렌계 공중합체의 제조방법, 프로필렌 중합체, 프로필렌계 중합체 조성물 및 이들의 용도
EP06746639.1A EP1900758B9 (fr) 2005-05-18 2006-05-18 Procédé de production d'une polyoléfine
KR1020117015073A KR101169179B1 (ko) 2005-05-18 2006-05-18 올레핀 중합용 촉매, 올레핀 중합체의 제조방법, 프로필렌계 공중합체의 제조방법, 프로필렌 중합체, 프로필렌계 중합체 조성물 및 이들의 용도
KR1020107009102A KR101064037B1 (ko) 2005-05-18 2006-05-18 올레핀 중합용 촉매, 올레핀 중합체의 제조방법, 프로필렌계 공중합체의 제조방법, 프로필렌 중합체, 프로필렌계 중합체 조성물 및 이들의 용도
US11/984,440 US9382356B2 (en) 2005-05-18 2007-11-16 Catalyst for olefin polymerization, method for producing olefin polymer, method for producing propylene-based copolymer, propylene polymer, propylene-based polymer composition, and use of those
US15/174,421 US20160280819A1 (en) 2005-05-18 2016-06-06 Catalyst for olefin polymerization, method for producing olefin polymer, method for producing propylene-based copolymer, propylene polymer, propylene-based polymer composition, and use of those

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SG10201504176PA (en) 2015-06-29
EP2275451B1 (fr) 2016-10-19
EP1900758B9 (fr) 2016-07-13
US20160280819A1 (en) 2016-09-29
EP2275457A2 (fr) 2011-01-19
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US9382356B2 (en) 2016-07-05
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KR20110095396A (ko) 2011-08-24
TW200710107A (en) 2007-03-16
EP1900758B1 (fr) 2016-03-16
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KR101044214B1 (ko) 2011-06-29
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EP1900758A1 (fr) 2008-03-19
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